FR3157133A1 - Hair coloring process using a lightening composition and a coloring composition comprising a direct dye, an aromatic compound and a hydroxylated aliphatic solvent. - Google Patents

Abstract

A method for coloring hair using a lightening composition and a coloring composition comprising a direct dye, an aromatic compound, and a hydroxylated aliphatic solvent. The invention relates to a method for coloring keratin fibers, in particular human keratin fibers such as hair, comprising the application to said keratin fibers of a lightening composition and a coloring composition comprising: - one or more direct dyes, - one or more compounds of formula (I): (I) in which Y represents a C1-C4 hydroxyalkyl group or a C1-C4 hydroxyalkyloxy radical, n denotes an integer ranging from 0 to 5, X, which may be identical or different, represents a C1-C4 alkyl radical or a halogen, - one or more aliphatic hydroxylated solvents comprising from 2 to 6 carbon atoms.

Description

Hair coloring process using a lightening composition and a coloring composition comprising a direct dye, an aromatic compound and a hydroxylated aliphatic solvent.

The subject of the present invention is a process for coloring human keratin fibers, in particular hair, using a lightening composition and a coloring composition comprising a direct dye, an aromatic compound and a hydroxylated aliphatic solvent as well as a multi-compartment device containing the compositions.

There are two main ways of coloring human keratin fibers, and in particular hair.

One of these two methods is oxidation or permanent coloring. This coloring method uses one or more oxidation dye precursors, usually one or more oxidation bases possibly associated with one or more couplers.

In general, oxidation bases are chosen from ortho- or para-phenylenediamines, ortho- or para-aminophenols and heterocyclic compounds. These oxidation bases are colorless or weakly colored compounds which, when combined with oxidizing products, allow access to colored species.

Very often, the shades obtained with these oxidation bases are varied by combining them with one or more couplers, the latter being chosen in particular from aromatic meta-diamines, meta-aminophenols, meta-diphenols and certain heterocyclic compounds, such as indole compounds.

The variety of molecules involved in the oxidation bases and couplers allows for a rich palette of colors. This type of coloring also allows for permanent colors.

The second method of coloring, called direct or semi-permanent coloring, involves the application of direct dyes which are molecules having an affinity for fibers and coloring even in the absence of an oxidizing agent added to the compositions containing them. Given the nature of the molecules used, these remain on the surface of the fiber and penetrate relatively little into the fiber, compared to the small molecules of oxidation dye precursors.

The direct dyes generally used are chosen from nitrobenzene, anthraquinone, nitropyridine, azo, methine, azomethine, xanthene, acridine, azine or triarylmethane direct dyes. The chemical species used can be non-ionic, anionic (acid dyes) or cationic (basic dyes). Direct dyes can also be natural dyes.

Compositions containing one or more direct dyes are applied to the keratin fibers for a time necessary to obtain the desired color, then rinsed.

However, the resulting colorations are particularly chromatic but temporary or semi-permanent because their desorption from the surface and/or the core of the fiber is responsible for their lack of tinctorial power and their poor resistance to washing.

There is a need to achieve permanent hair coloring, without oxidation dyes such as bases and couplers, in natural shades, with a harmonious and natural coloring result.

There is also a need to obtain a hair coloring which is capable of leading to good color build-up, intensity and chromaticity, while having low selectivity and good tenacity, in particular good remanence to shampoos, and which is capable of leading to good tinctorial performances, even after a storage period, while having good qualities of use and retaining good sensory performances in particular in terms of shine, softness, flexibility, smoothing, detangling of keratin fibers such as hair.

This aim and others are achieved by the present invention which therefore relates to a process for coloring keratin fibers, in particular human keratin fibers such as hair, comprising the application to said keratin fibers:
(i) a lightening composition comprising:
- one or more oxidizing agent(s),
- one or more alkaline agent(s); and
ii) a coloring composition comprising:
- one or more direct dye(s),
- one or more compound(s) of formula (I):
(I)
in which Y represents a C ₁ -C ₄ hydroxyalkyl group or a C ₁ -C ₄ hydroxyalkyloxy radical, n denotes an integer ranging from 0 to 5, X, identical or different, represents a C ₁ -C ₄ alkyl radical or a halogen,
- one or more aliphatic hydroxylated solvent(s) comprising from 2 to 6 carbon atoms.

The invention also relates to a device with at least three compartments, for coloring keratin fibers, comprising at least a first compartment containing a coloring composition comprising one or more direct dye(s), one or more compound(s) of formula (I) as defined above and one or more aliphatic hydroxylated solvent(s) comprising from 2 to 6 carbon atoms, at least a second compartment containing an alkaline composition comprising one or more alkaline agent(s), and at least a third compartment containing an oxidizing composition comprising one or more chemical oxidizing agent(s).

The invention makes it possible to obtain colorations of keratin fibers with good tenacity, in particular good remanence to shampoos, in natural shades, without using oxidation dyes such as bases and couplers, with a harmonious, natural coloring result, that is to say without a helmet effect, while providing shine.

Other objects, characteristics, aspects and advantages of the invention will appear even more clearly on reading the description and examples which follow and on examining the attached drawing, in which:

In what follows, and unless otherwise indicated, the limits of a domain of values are included in this domain, in particular in the expressions “between” and “ranging from … to …”.

Furthermore, the expression “at least one” used in this description is equivalent to the expression “one or more”.

As previously stated, the coloring process involves a lightening composition and a coloring composition.

Lightening composition

The terms "lightening" and "bleaching" are synonymous and can be used interchangeably.

The lightening composition comprises one or more chemical oxidizing agent(s) and one or more alkaline agent(s).

Chemical oxidizing agent

The lightening composition used in the process according to the invention comprises one or more chemical oxidizing agent(s).

A chemical oxidizing agent is an oxidizing agent other than oxygen in the air.

The chemical oxidizing agent(s) are chosen from hydrogen peroxide, urea peroxide, alkali metal bromates or ferricyanides, peroxygenated salts such as alkali or alkaline earth metal persulfates, perborates and percarbonates, and peracids and their precursors.

Preferably, the lightening composition does not comprise peroxygenated salts such as persulfates, perborates and percarbonates of alkali or alkaline earth metals.

More preferably, the composition according to the invention comprises hydrogen peroxide.

The total content of the chemical oxidizing agent(s) preferably varies from 1 to 40% by weight, more preferably from 2 to 30% by weight, better still from 3 to 20% by weight relative to the total weight of the lightening composition.

Alkaline agent

The lightening composition used in the method according to the invention comprises one or more alkaline agents which may be mineral, organic or hybrid alkaline agents.

For the purposes of the present invention, the terms “alkaline agent” or “alkalizing agent” are used interchangeably.

The mineral alkalizing agent(s) are preferably chosen from ammonia, alkali carbonates or bicarbonates such as sodium (hydrogen)carbonate and potassium (hydrogen)carbonate, alkali or alkaline earth metal phosphates such as sodium phosphates or potassium phosphates, sodium or potassium hydroxides, alkali or alkaline earth metal silicates or metasilicates such as sodium metasilicate and mixtures thereof.

The organic alkalizing agent(s) are preferably chosen from alkanolamines, amino acids, organic amines other than alkanolamines, oxyethylenated and/or oxypropylenated ethylenediamines, 1,3 diaminopropane, spermine, spermidine and mixtures thereof.

By alkanolamine is meant an organic amine comprising a primary, secondary or tertiary amine function, and one or more linear or branched _C1 - _C8 alkyl groups carrying one or more hydroxyl radicals.

Particularly suitable for carrying out the invention are organic amines chosen from alkanolamines such as mono-, di- or tri-alkanolamines, comprising one to three hydroxyalkyl radicals, identical or not, in C ₁ -C ₄ .

In particular, the alkanolamine(s) are chosen from monoethanolamine (MEA), diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, N,N-dimethylethanolamine, 2-amino-2-methyl-1-propanol, triisopropanolamine, 2-amino-2-methyl-1,3-propanediol, 3-amino-1,2-propanediol, 3-dimethylamino-1,2-propanediol, tris-hydroxymethylamino-methane and mixtures thereof.

Advantageously, the amino acids are basic amino acids comprising an additional amine function. Such basic amino acids are preferably chosen from histidine, lysine, arginine, ornithine, citrulline.

The organic amine may also be chosen from heterocyclic organic amines. In addition to histidine already mentioned in the amino acids, mention may in particular be made of pyridine, piperidine, imidazole, triazole, tetrazole and benzimidazole. The organic amine may also be chosen from amino acid dipeptides. As amino acid dipeptides which may be used in the present invention, mention may in particular be made of carnosine, anserine and balenine. The organic amine may also be chosen from compounds comprising a guanidine function. As amines of this type other than arginine which may be used in the present invention, mention may in particular be made of creatine, creatinine, 1,1-dimethylguanidine, 1,1-diethylguanidine, glycocyamine, metformin, agmatine, n-amidinoalanine, 3-guanidinopropionic acid, 4-guanidinobutyric acid and 2-([amino(imino)methyl]amino)ethane-1-sulfonic acid.)

As hybrid compounds, guanidine carbonate or monoethanolamine hydrochloride can be used in particular.

The alkaline agent(s) useful according to the invention is (are) preferably chosen from alkanolamines such as monoethanolamine, diethanolamine, triethanolamine; ammonia, carbonates or bicarbonates such as sodium (hydrogen)carbonate and potassium (hydrogen)carbonates, silicates or metasilicates of alkali or alkaline earth metals such as sodium metasilicate and their mixtures, more preferably from alkanolamines and ammonia, better still from alkanolamines, even better still, monoethanolamine.

In a particular embodiment, the lightening composition used in the method according to the invention is free of ammonia.

The total content of the alkaline agent(s) preferably varies from 0.1 to 40% by weight, more preferably from 1 to 30% by weight, better still from 2 to 25% by weight, even better still from 4 to 20% by weight relative to the total weight of the lightening composition.

According to a particular embodiment, the total content of alkanolamine, preferably monoethanolamine, preferably varies from 0.1 to 40% by weight, more preferably from 1 to 30% by weight, better still from 2 to 25% by weight, even better still from 4 to 20% by weight, or even from 5 to 15% by weight relative to the total weight of the lightening composition.

Fatty acid

The lightening composition used in the method according to the invention may also comprise one or more fatty acids.

Preferably, the lightening composition used in the method according to the invention comprises one or more fatty acid(s).

By “fatty acids” is meant a long-chain carboxylic acid comprising at least 6 carbon atoms, in particular from 6 to 40 carbon atoms, preferably from 8 to 30 carbon atoms. The fatty acids according to the invention preferably comprise from 10 to 30 carbon atoms and better still from 12 to 22 carbon atoms. They may optionally be hydroxylated.

Preferably, the fatty acids comprise at least one carboxylic acid group and an alkyl chain, linear or branched, saturated or unsaturated, in particular unsaturated, comprising from 6 to 40 carbon atoms, preferably from 8 to 30 carbon atoms, more preferably from 10 to 30 carbon atoms and better still from 12 to 22 carbon atoms.

Preferably, the fatty acids comprise at least one carboxylic acid group and an alkyl chain, linear or branched, saturated or unsaturated, in particular unsaturated, comprising from 10 to 30 carbon atoms, in particular from 12 to 22 carbon atoms.

Preferably, the fatty acids comprise at least one carboxylic acid group and an unsaturated, linear or branched alkyl chain comprising from 12 to 22 carbon atoms.

More preferably, the fatty acids according to the invention are chosen from compounds of structure R-C(O)OH in which R represents an alkyl group, linear or branched, saturated or unsaturated, comprising from 6 to 40 carbon atoms, preferably from 8 to 30 carbon atoms, preferentially from 10 to 24 carbon atoms, better still from 12 to 20 carbon atoms.

For the purposes of the present invention, the fatty acids present in the composition are neither oxyalkylenated nor glycerolated.

Fatty acids can be chosen from solid fatty acids, liquid fatty acids and their mixtures.

For the purposes of the present invention, the term "solid fatty acid" means a fatty acid having a melting point greater than 25°C, preferably greater than or equal to 28°C, more preferably greater than or equal to 30°C at atmospheric pressure (1,013.105 Pa).

The solid fatty acids used in the present invention are notably chosen from myristic acid, cetyl acid, arachidic acid, stearic acid, lauric acid, behenic acid, 12-hydroxystearic acid and mixtures thereof.

Particularly preferably, the solid fatty acid(s) are chosen from lauric acid, myristic acid, cetyl acid, stearic acid.

For the purposes of the present invention, the term “liquid fatty acid” means a fatty acid having a melting point of less than or equal to 25°C, preferably less than or equal to 20°C at atmospheric pressure (1,013.105 Pa).

The liquid fatty acid(s) according to the invention may be chosen from oleic acid, linoleic acid, arachidonic acid, isostearic acid, isopalmitic acid, and mixtures thereof, preferably oleic acid.

Preferably, the lightening composition comprises one or more solid fatty acid(s), preferably chosen from lauric acid, myristic acid, cetyl acid, stearic acid and mixtures thereof.

Advantageously, the fatty acid(s) are present in a total content ranging from 0.1 to 15% by weight, preferably from 0.5 to 10%, preferentially from 1 to 5% by weight relative to the total weight of the lightening composition.

Fatty substances other than fatty acids

The lightening composition used in the method according to the invention may also comprise one or more fatty substances other than fatty acids.

Preferably, the lightening composition used in the method according to the invention comprises one or more fatty substances other than fatty acids.

By "fatty substance" is meant an organic compound insoluble in water at 25°C and at atmospheric pressure (1,013.105 Pa) (solubility less than 5% by weight, and preferably less than 1% by weight, even more preferably less than 0.1% by weight). They have in their structure at least one hydrocarbon chain comprising at least 6 carbon atoms and/or a chain of at least two siloxane groups. In addition, fatty substances are generally soluble in organic solvents under the same temperature and pressure conditions, such as for example chloroform, dichloromethane, carbon tetrachloride, ethanol, benzene, toluene, tetrahydrofuran (THF), vaseline oil or decamethylcyclopentasiloxane.

Advantageously, the fatty substances which can be used in the present invention are neither (poly)oxyalkylenated nor (poly)glycerolated.

Preferably, the fatty substances useful according to the invention are non-silicone.

The term “non-silicone fatty substance” means a fatty substance not containing Si-O bonds and the term “silicone fatty substance” means a fatty substance containing at least one Si-O bond.

The fatty substances useful according to the invention may be liquid fatty substances (or oils) and/or solid fatty substances. Liquid fatty substance means a fatty substance having a melting point less than or equal to 25°C and at atmospheric pressure (1,013.105 Pa). Solid fatty substance means a fatty substance having a melting point greater than 25°C at atmospheric pressure (1,013.105 Pa).

For the purposes of the present invention, the melting point corresponds to the temperature of the most endothermic peak observed in thermal analysis (differential scanning calorimetry or DSC) as described in the ISO 11357-3; 1999 standard. The melting point can be measured using a differential scanning calorimeter (DSC), for example the calorimeter sold under the name “MDSC 2920” by the company TA Instruments. In the present application, all melting points are determined at atmospheric pressure (1,013.105 Pa).

More particularly, the liquid fatty body(ies) according to the invention are chosen from C ₆ to C ₁₆ liquid hydrocarbons, liquid hydrocarbons comprising more than 16 carbon atoms, non-silicone oils of animal origin, triglyceride type oils of vegetable or synthetic origin, fluorinated oils, liquid fatty alcohols, liquid esters of fatty acid and/or fatty alcohol other than triglycerides, silicone oils, and mixtures thereof.

It is recalled that alcohols, esters and fatty acids more particularly have at least one hydrocarbon group, linear or branched, saturated or unsaturated, comprising from 6 to 40, better still from 8 to 30 carbon atoms, optionally substituted, in particular by one or more hydroxyl groups (in particular 1 to 4). If they are unsaturated, these compounds may comprise one to three carbon-carbon double bonds, conjugated or not.

With regard to liquid C ₆ to C ₁₆ hydrocarbons, the latter may be linear, branched, optionally cyclic, and are preferably chosen from alkanes. For example, mention may be made of hexane, cyclohexane, undecane, dodecane, isododecane, tridecane, isoparaffins such as isohexadecane, isodecane, and mixtures thereof.

Liquid hydrocarbons comprising more than 16 carbon atoms may be linear or branched, of mineral or synthetic origin, and are preferably chosen from paraffin or vaseline oils (INCI name mineral oil or paraffinum liquidum), polydecenes, hydrogenated polyisobutene such as Parléam®, and their mixtures.

As hydrocarbon oils of animal origin, we can cite perhydrosqualene.

Triglyceride oils of vegetable or synthetic origin are preferably chosen from liquid triglycerides of fatty acids containing 6 to 30 carbon atoms such as triglycerides of heptanoic or octanoic acids or, for example, sunflower, corn, soybean, pumpkin, grape seed, sesame, hazelnut, apricot, macadamia, arara, sunflower, castor, avocado oils, triglycerides of caprylic/capric acids such as those sold by the company Stearineries Dubois or those sold under the names Miglyol® 810, 812 and 818 by the company Dynamit Nobel, shea butter oil, and mixtures thereof.

As regards fluorinated oils, these may be chosen from perfluoromethylcyclopentane and perfluoro-1,3 dimethylcyclohexane, sold under the names “FLUTEC® PC1” and “FLUTEC® PC3” by the company BNFL Fluorochemicals; perfluoro-1,2-dimethylcyclobutane; perfluoroalkanes such as dodecafluoropentane and tetradecafluorohexane, sold under the names “PF 5050®” and “PF 5060®” by the company 3M, or bromoperfluorooctyl sold under the name “FORALKYL®” by the company Atochem; nonafluoro-methoxybutane and nonafluoroethoxyisobutane; perfluoromorpholine derivatives, such as 4-trifluoromethyl perfluoromorpholine sold under the name “PF 5052®” by the company 3M.

The liquid fatty alcohols suitable for implementing the invention are more particularly chosen from saturated or unsaturated, linear or branched, preferably unsaturated or branched alcohols comprising from 6 to 40 carbon atoms, preferably from 8 to 30 carbon atoms. Examples that may be mentioned are octyldodecanol, 2-butyloctanol, 2-hexyldecanol, 2-undecylpentadecanol, isostearyl alcohol, oleyl alcohol, linolenic alcohol, ricinoleic alcohol, undecylenic alcohol or linoleic alcohol, and mixtures thereof.

As regards the liquid esters of fatty acids and/or fatty alcohols, other than the triglycerides mentioned above, mention may be made in particular of esters of saturated or unsaturated aliphatic mono or polyacids, linear in C ₁ to C ₂₆ or branched in C ₃ to C ₂₆ and of saturated or unsaturated aliphatic mono or polyalcohols, linear in C ₁ to C ₂₆ or branched in C ₃ to C ₂₆ , the total number of carbons of the esters being greater than or equal to 6, more advantageously greater than or equal to 10.

Preferably, for the monoalcohol esters, at least one of the alcohol or acid from which the esters of the invention are derived is branched.

Monoesters include dihydroabietyl behenate; octyldodecyl behenate; isocetyl behenate; isostearyl lactate; lauryl lactate; linoleyl lactate; oleyl lactate; isostearyl octanoate; isocetyl octanoate; octyl octanoate; decyl oleate; isocetyl isostearate; isocetyl laurate; isocetyl stearate; isodecyl octanoate; isodecyl oleate; isononyl isononanoate; isostearyl palmitate; methyl acetyl ricinoleate; octyl isononanoate; 2-ethylhexyl isononate; octyldodecyl erucate; oleyl erucate; ethyl and isopropyl palmitates, such as ethyl-2-hexyl palmitate, 2-octyldecyl palmitate; alkyl myristates such as isopropyl myristate; isobutyl stearate; 2-hexyldecyl laurate, and mixtures thereof.

Preferably, among the monoesters of monoacids and monoalcohols, ethyl and isopropyl palmitates, alkyl myristates such as isopropyl or ethyl myristate, isocetyl stearate, ethyl-2-hexyl isononanoate, isodecyl neopentanoate, isostearyl neopentanoate, and mixtures thereof will be used.

Still within the framework of this variant, it is also possible to use esters of C ₄ to C ₂₂ di or tricarboxylic acids and C ₁ to C ₂₂ alcohols and esters of mono-, di-, or tricarboxylic acids and C ₂ to C ₂₆ di-, tri-, tetra- or pentahydroxy alcohols.

Examples include: diethyl sebacate; diisopropyl sebacate; diisopropyl adipate; di-n-propyl adipate; dioctyl adipate; diisostearyl adipate; dioctyl maleate; glyceryl undecylenate; octyldodecyl stearoyl stearate; pentaerythrityl monoricinoleate; pentaerythrityl tetraisononanoate; pentaerythrityl tetrapelargonate; pentaerythrityl tetraisostearate; pentaerythrityl tetraoctanoate; propylene glycol dicaprylate; propylene glycol dicaprate, tridecyl erucate; triisopropyl citrate; triisotearyl citrate; glyceryl trilactate; glyceryl trioctanoate; trioctyldodecyl citrate; trioleyl citrate; propylene glycol dioctanoate; neopentyl glycol diheptanoate; diethylene glycol diisocyanate; polyethylene glycol distearates, and mixtures thereof.

The compositions may also comprise, as fatty ester, esters and diesters of sugars of C ₆ to C ₃₀ fatty acids, preferably C ₁₂ to C ₂₂ . It is recalled that the term "sugar" means oxygenated hydrocarbon compounds which have several alcohol functions, with or without aldehyde or ketone function, and which comprise at least 4 carbon atoms. These sugars may be monosaccharides, oligosaccharides or polysaccharides.

Suitable sugars include, for example, sucrose (or saccharose), glucose, galactose, ribose, fucose, maltose, fructose, mannose, arabinose, xylose, lactose, and their derivatives, in particular alkylated ones, such as methylated derivatives such as methylglucose.

The esters of sugars and fatty acids may be chosen in particular from the group comprising the esters or mixtures of esters of sugars described above and of C ₆ to C ₃₀ fatty acids, preferably C ₁₂ to C ₂₂ , linear or branched, saturated or unsaturated. If they are unsaturated, these compounds may comprise one to three carbon-carbon double bonds, conjugated or not.

The esters according to this variant can also be chosen from mono-, di-, tri- and tetra-esters, polyesters and their mixtures.

These esters may be, for example, oleate, laurate, palmitate, myristate, behenate, cocoate, stearate, linoleate, linolenate, caprate, arachidonate, or mixtures thereof, such as in particular the mixed esters oleo-palmitate, oleo-stearate, palmito-stearate.

More particularly, mono- and di-esters are used, and in particular mono- or di-oleate, stearate, behenate, oleopalmitate, linoleate, linolenate, oleostearate, of sucrose, glucose or methylglucose, and mixtures thereof.

An example is the product sold under the name Glucate® DO by the company Amerchol, which is a methylglucose dioleate.

Preferably, a liquid ester of monobasic acid and monoalcohol will be used.

The solid fatty bodies according to the invention preferably have a viscosity greater than 2 Pa.s, measured at 25°C and at a shear rate of 1 s ^-1 .

The solid fatty body(ies) are preferably chosen from solid fatty alcohols, solid esters of fatty acids and/or fatty alcohols, waxes, ceramides, and mixtures thereof.

By "fatty alcohol" is meant a long-chain aliphatic alcohol comprising from 6 to 40 carbon atoms, preferably from 8 to 30 carbon atoms and comprising at least one hydroxyl group OH. These fatty alcohols are neither oxyalkylenated nor glycerolated.

The solid fatty alcohols may be saturated or unsaturated, linear or branched, and comprise from 8 to 40 carbon atoms, preferably from 10 to 30 carbon atoms. Preferably, the solid fatty alcohols have the structure R-OH with R denoting a linear alkyl group, optionally substituted by one or more hydroxyl groups, comprising from 8 to 40, preferably from 10 to 30 carbon atoms, better still from 10 to 30, or even from 12 to 24 atoms, even better still from 14 to 22 carbon atoms.

The solid fatty alcohols that may be used are preferably chosen from saturated or unsaturated, linear or branched (mono)alcohols, preferably linear and saturated, containing from 8 to 40 carbon atoms, better still from 10 to 30, or even from 12 to 24 atoms, even better still from 14 to 22 carbon atoms.

The solid fatty alcohols that may be used may be chosen from, alone or in a mixture: myristic or myristyl alcohol (or 1-tetradecanol); cetyl alcohol (or 1-hexadecanol); stearyl alcohol (or 1-octadecanol); arachidyl alcohol (or 1-eicosanol); behenyl alcohol (or 1-docosanol); lignoceryl alcohol (or 1-tetracosanol); ceryl alcohol (or 1-hexacosanol); montanyl alcohol (or 1-octacosanol); myricyl alcohol (or 1-triacontanol).

Preferably, the solid fatty alcohol is chosen from cetyl alcohol, stearyl alcohol, behenyl alcohol, myristyl alcohol, arachidyl alcohol and mixtures thereof, such as cetylstearyl or cetearyl alcohol. In a particularly preferred manner, the solid fatty alcohol is chosen from cetylstearyl or cetearyl alcohol and cetyl alcohol.

The solid fatty acid and/or fatty alcohol esters that may be used are preferably chosen from esters derived from C ₉ -C ₂₆ carboxylic fatty acid and/or C ₉ -C ₂₆ fatty alcohol.

Preferably, these solid fatty esters are esters of a saturated, linear or branched carboxylic acid containing at least 10 carbon atoms, preferably 10 to 30 carbon atoms and more particularly 12 to 24 carbon atoms, and of a saturated, linear or branched monoalcohol containing at least 10 carbon atoms, preferably 10 to 30 carbon atoms and more particularly 12 to 24 carbon atoms. The saturated carboxylic acids may optionally be hydroxylated, and are preferably monocarboxylic acids.

Esters of C ₄ -C ₂₂ di- or tricarboxylic acids and C ₁ -C ₂₂ alcohols and esters of mono-, di- or tricarboxylic acids and C ₂ -C ₂₆ di-, tri-, tetra- or pentahydroxylated alcohols may also be used.

Examples include octyldodecyl behenate, isocetyl behenate, cetyl lactate, stearyl octanoate, octyl octanoate, cetyl octanoate, decyl oleate, hexyl stearate, octyl stearate, myristyl stearate, cetyl stearate, stearyl stearate, octyl pelargonate, cetyl myristate, myristyl myristate, stearyl myristate, diethyl sebacate, diisopropyl sebacate, diisopropyl adipate, di n-propyl adipate, dioctyl adipate, dioctyl maleate, dioctyl, octyl palmitate, myristyl palmitate, cetyl palmitate, stearyl palmitate, and mixtures thereof.

Preferably, the solid fatty acid and/or fatty alcohol esters are chosen from C ₉ -C ₂₆ alkyl palmitates, in particular myristyl, cetyl and stearyl palmitates; C ₉ -C ₂₆ alkyl myristates such as cetyl myristate, stearyl myristate and myristyl myristate; C ₉ -C ₂₆ alkyl stearates, in particular myristyl, cetyl and stearyl stearates; and mixtures thereof.

A wax, within the meaning of the present invention, is a lipophilic compound, solid at 25°C and atmospheric pressure, with a reversible solid/liquid state change, having a melting point above about 40°C and up to 200°C, and having an anisotropic crystalline organization in the solid state. Generally speaking, the size of the wax crystals is such that the crystals diffract and/or scatter light, giving the composition comprising them a more or less opaque cloudy appearance. By bringing the wax to its melting temperature, it is possible to make it miscible with oils and to form a microscopically homogeneous mixture, but by bringing the temperature of the mixture back to room temperature, a recrystallization of the wax is obtained, detectable microscopically and macroscopically (opalescence).

In particular, the waxes suitable for the invention may be chosen from waxes of animal, vegetable, mineral origin, non-silicone synthetic waxes and their mixtures.

Examples include hydrocarbon waxes, such as beeswax, especially of biological origin, lanolin wax, and Chinese insect waxes; rice bran wax, carnauba wax, candelilla wax, ouricury wax, alfa wax, berry wax, shellac wax, japan wax and sumac wax; montan wax, orange and lemon waxes, microcrystalline waxes, paraffins and ozokerite; polyethylene waxes, waxes obtained by Fisher-Tropsch synthesis and waxy copolymers, as well as their esters.

We can also mention microcrystalline waxes from _C20 to _C60 , such as Microwax HW.

We can also mention the PM 500 polyethylene wax marketed under the reference Permalen 50-L polyethylene.

Mention may also be made of waxes obtained by catalytic hydrogenation of animal or vegetable oils having linear or branched fatty chains, from C ₈ to C ₃₂ . Among these, mention may in particular be made of isomerized jojoba oil, such as trans isomerized partially hydrogenated jojoba oil, in particular that manufactured or marketed by the company Desert Whale under the commercial reference Iso-Jojoba-50 ^® , hydrogenated sunflower oil, hydrogenated castor oil, hydrogenated coconut oil, hydrogenated lanolin oil, and di-(trimethylol-1,1,1 propane) tetrastearate, in particular that sold under the name Hest 2T-4S ^® by the company HETERENE.

Waxes obtained by hydrogenation of castor oil esterified with cetyl alcohol can also be used, such as those sold under the names Phytowax ricin 16L64 ^® and 22L73 ^® by the company SOPHIM.

As a wax, a C ₂₀ to C ₄₀ alkyl (hydroxystearyloxy) stearate (the alkyl group comprising 20 to 40 carbon atoms) can also be used, alone or in a mixture. Such a wax is sold in particular under the names "Kester Wax K 82 P ^® ", "Hydroxypolyester K 82 P ^® " and "Kester Wax K 80 P®" by the company KOSTER KEUNEN.

It is also possible to use microwaxes in the compositions of the invention; we can cite in particular carnauba microwaxes, such as that marketed under the name MicroCare 350 ^® by the company MICRO POWDERS, synthetic wax microwaxes, such as that marketed under the name MicroEase 114S® by the company MICRO POWDERS, microwaxes consisting of a mixture of carnauba wax and polyethylene wax, such as those marketed under the names Micro Care 300 ^® and 310 ^® by the company MICRO POWDERS, microwaxes consisting of a mixture of carnauba wax and synthetic wax, such as that marketed under the name Micro Care 325 ^® by the company MICRO POWDERS, polyethylene microwaxes, such as those marketed under the names Micropoly 200 ^® , 220 ^® , 220L ^® and 250S ^® by the company MICRO POWDERS and microwaxes of polytetrafluoroethylene, such as those marketed under the names Microslip 519 ^® and 519 L ^® by the company MICRO POWDERS.

The waxes are preferably chosen from mineral waxes such as paraffin wax, vaseline wax, lignite wax or ozokerite; vegetable waxes such as cocoa butter or cork or sugar cane fiber waxes, olive wax, rice wax, hydrogenated jojoba wax, Ouricoury wax, Carnauba wax, Candelila wax, Alfa wax, or absolute flower waxes such as blackcurrant flower essential wax sold by the company BERTIN (France); waxes of animal origin such as beeswax or modified beeswax (cerabellina), spermaceti, lanolin wax and lanolin derivatives; microcrystalline waxes; and mixtures thereof.

Ceramides or ceramide analogues such as glycoceramides, which may be used in the compositions according to the invention, are known; mention may be made in particular of ceramides of classes I, II, III and V according to the DAWNING classification.

The ceramides or their analogues which may be used preferably correspond to the following formula: R ₃ CH(OH)CH(CH ₂ OR ₂ )(NHCOR ₁ ), in which:
R ₁ denotes a linear or branched, saturated or unsaturated alkyl group derived from C ₁₄ -C ₃₀ fatty acids, this group possibly being substituted by a hydroxyl group in the alpha position, or a hydroxyl group in the omega position esterified by a saturated or unsaturated C ₁₆ -C ₃₀ fatty acid;
R ₂ denotes a hydrogen atom, a (glycosyl)n group, a (galactosyl)m group or a sulfogalactosyl group, in which n is an integer ranging from 1 to 4 and m is an integer ranging from 1 to 8;
R ₃ denotes a C ₁₅ -C ₂₆ hydrocarbon group, saturated or unsaturated in the alpha position, this group possibly being substituted by one or more C ₁ -C ₁₄ alkyl groups; it being understood that in the case of natural ceramides or glycoceramides, R ₃ may also denote a C ₁₅ -C ₂₆ alpha-hydroxyalkyl group, the hydroxyl group being optionally esterified by a C ₁₆ -C ₃₀ alpha-hydroxy acid.

More particularly preferred ceramides are compounds for which R ₁ denotes a saturated or unsaturated alkyl derived from C ₁₆ -C ₂₂ fatty acids; R ₂ denotes a hydrogen atom and R ₃ denotes a linear saturated C ₁₅ group.

Preferably, ceramides are used for which R ₁ denotes a saturated or unsaturated alkyl group derived from C ₁₄ -C ₃₀ fatty acids; R ₂ denotes a galactosyl or sulfogalactosyl group; and R ₃ denotes a -CH=CH-(CH ₂ ) ₁₂ -CH ₃ group.

It is also possible to use compounds for which R ₁ denotes a saturated or unsaturated alkyl radical derived from C ₁₂ -C ₂₂ fatty acids; R ₂ denotes a galactosyl or sulfogalactosyl radical and R ₃ denotes a saturated or unsaturated C ₁₂ -C ₂₂ hydrocarbon radical and preferably a -CH=CH-(CH ₂ ) ₁₂ -CH ₃ group.

Particularly preferred compounds that may also be mentioned are 2-N-linoleoylamino-octadecane-1,3-diol; 2-N-oleoylamino-octadecane-1,3-diol; 2-N-palmitoylamino-octadecane-1,3-diol; 2-N-stearoylamino-octadecane-1,3-diol; 2-N-behenoylamino-octadecane-1,3-diol; 2-N-[2-hydroxy-palmitoyl]-amino-octadecane-1,3-diol; 2-N-stearoyl amino-octadecane-1,3,4 triol and in particular N-stearoyl phytosphingosine 2-N-palmitoylamino-hexadecane-1,3-diol, N-linoleoyldihydrosphingosine, N-oleoyldihydrosphingosine, N-palmitoyldihydrosphingosine, N-stearoyldihydrosphingosine, and N-behenoyldihydrosphingosine, N-docosanoyl N-methyl-D-glucamine, N-(2-hydroxyethyl)-N-(3-cetyloxy-2-hydroxypropyl)cetyl acid amide and bis-(N-hydroxyethyl N-cetyl) malonamide; and mixtures thereof. Preferably, N-oleoyldihydrosphingosine will be used.

The solid fatty bodies are preferably chosen from solid fatty alcohols, solid esters of fatty acids and/or fatty alcohols and their mixtures.

According to a preferred embodiment, the lightening composition used in the method according to the invention comprises at least one solid fatty substance, preferably chosen from solid fatty alcohols, solid esters of fatty acids and/or fatty alcohols and their mixtures.

When present, the fatty substance(s) other than fatty acids are preferably present in the lightening composition in a total content ranging from 2 to 40% by weight, preferably from 3 to 35% by weight, more preferably from 4 to 30% by weight, better still from 5 to 25% by weight, relative to the total weight of the lightening composition.

Surfactants other than fatty acids

The lightening composition used in the method according to the invention may also comprise one or more surfactants other than fatty acids.

Preferably, the lightening composition used in the method according to the invention comprises one or more surfactants other than fatty acids.

These may preferably be chosen from anionic surfactants, amphoteric surfactants, non-ionic surfactants, cationic surfactants and/or mixtures thereof, more preferably from anionic surfactants, non-ionic surfactants and/or mixtures thereof.

Preferably, the lightening composition used in the method according to the invention comprises one or more non-ionic surfactants.

The non-ionic surfactant(s) which can be used in the lightening composition used in the process of the present invention are described in particular, for example, in “Handbook of Surfactants” by M.R. PORTER, published by Blackie & Son (Glasgow and London), 1991, pp. 116-178.

Examples of non-ionic surfactants include the following compounds, alone or in mixtures:
- oxyalkylenated alkyl(C ₈ -C ₂₄ )phenols;
- _C8 to _C40 alcohols, saturated or unsaturated, linear or branched, oxyalkylenated or glycerolated, they preferably comprise one or two fatty chains;
- _C8 to _C30 fatty acid amides, saturated or unsaturated, linear or branched, oxyalkylenated;
- esters of _C8 to _C30 acids, saturated or unsaturated, linear or branched, and of polyethylene glycols;
- esters of fatty acids and sucrose,
- esters of _C8 to _C30 acids, saturated or unsaturated, linear or branched, and of sorbitol, preferably oxyethylenated;
- esters of saturated or unsaturated, linear or branched _C8 - _C30 fatty acids and glycerol;
- _C8 - _C30 fatty acid esters of sorbitan,
- _C8 - _C30 fatty acid esters of polyoxyethylenated sorbitan,
- alkyl(C ₈ -C ₃₀ )(poly)glucosides, alkenyl(C ₈ -C ₃₀ )(poly)glucosides, optionally oxyalkylenated (0 to 10 oxyalkylenated units) and comprising from 1 to 15 glucose units, alkyl(C ₈ -C ₃₀ )(poly)glucoside esters,
- oxyethylenated vegetable oils, saturated or not;
- ethylene oxide and/or propylene oxide condensates;
- derivatives of N -alkyl(C ₈ -C ₃₀ )glucamine and N -acyl(C ₈ -C ₃₀ )-methylglucamine;
- amine oxides.

They are chosen, in particular, from alcohols, alpha-diols, alkyl(C ₁ -C ₂₀ )phenols, these compounds being ethoxylated, propoxylated or glycerolated, and having at least one fatty chain comprising, for example, from 8 to 24 carbon atoms, preferably from 8 to 18 carbon atoms, the number of ethylene oxide or propylene oxide groups being able to range in particular from 1 to 200 and the number of glycerol groups being able to range in particular from 1 to 30.

Mention may also be made of condensates of ethylene oxide and propylene oxide on fatty alcohols; ethoxylated fatty amides preferably having from 1 to 30 ethylene oxide units, polyglycerolated fatty amides comprising on average from 1 to 5 glycerol groups and in particular from 1.5 to 4, sucrose fatty acid esters, polyethylene glycol fatty acid esters, oxyethylenated vegetable oils, N-(C ₆ -C ₂₄ alkyl)glucamine derivatives, amine oxides such as (C ₁₀ -C ₁₄ alkyl)amine oxides or N-(C ₁₀ -C ₁₄ acyl)-aminopropylmorpholine oxides.

The esters (in particular mono, di, tri esters) of _C8 - _C30 fatty acid, preferably _C12 - _C22 , and of sorbitan may be chosen from:
Sorbitan Caprylate; Sorbitan Cocoate; Sorbitan Isostearate; Sorbitan Laurate; Sorbitan Oleate; Sorbitan Palmitate; Sorbitan Stearate; Sorbitan Diisostearate; Sorbitan Dioleate; Sorbitan Distearate; Sorbitan Sesquicaprylate; Sorbitan Sesquiisostearate; Sorbitan Sesquioleate; Sorbitan Sesquistearate; Sorbitan Triisostearate; Sorbitan Trioleate; Sorbitan Tristearate.

The esters (in particular mono, di, triesters) of C ₈ -C ₃₀ fatty acids and of polyoxyethylenated sorbitan are preferably chosen from ester(s) of C ₈ -C ₃₀ fatty acid and of oxyethylenated sorbitan having from 1 to 30 ethylene oxide units, preferably from 2 to 20 ethylene oxide units, more preferably from 2 to 10 ethylene oxide units.

Preferably, the ester(s) of C ₈ -C ₃₀ fatty acid and of oxyethylenated sorbitan is/are chosen from esters of C ₁₂ -C ₁₈ fatty acids and of oxyethylenated sorbitan, in particular from esters of lauric acid, myristic acid, cetyl acid and stearic acid and of oxyethylenated sorbitan.

Preferably, the C ₈ -C ₃₀ fatty acid ester(s) of oxyethylenated sorbitan is/are chosen from oxyethylenated sorbitan monolaurate (4 EO) (POLYSORBATE-21), oxyethylenated sorbitan monolaurate (20 EO) (POLYSORBATE-20), oxyethylenated sorbitan monopalmitate (20 EO) (POLYSORBATE-40), oxyethylenated sorbitan monostearate (20 EO) (POLYSORBATE-60), oxyethylenated sorbitan monostearate (4 EO) (POLYSORBATE-61), oxyethylenated sorbitan monooleate (20 EO) (POLYSORBATE-80), oxyethylenated sorbitan monooleate (5 EO) (POLYSORBATE-81), oxyethylenated sorbitan tristearate (20 EO) (POLYSORBATE-65), oxyethylenated sorbitan trioleate (20 EO) (POLYSORBATE-85).

The nonionic surfactant(s) are preferably chosen from ethoxylated C ₈ -C ₂₄ fatty alcohols comprising from 1 to 200 ethylene oxide groups, preferably from 1 to 50 ethylene oxide groups, (C ₆ -C ₂₄ alkyl)polyglycosides, esters of saturated or unsaturated, linear or branched C ₈ -C ₃₀ fatty acids and of glycerol, esters of C ₈ -C ₃₀ fatty acids and of oxyethylenated sorbitan, and mixtures thereof, preferably from ethoxylated C ₈ -C ₂₄ fatty alcohols comprising from 1 to 50 ethylene oxide groups, (C ₆ -C ₂₄ alkyl)polyglycosides, esters of saturated or unsaturated, linear or branched C ₈ -C ₃₀ fatty acids, and of glycerol.

More preferably, the non-ionic surfactant(s) are chosen from ethoxylated _C8 - _C24 fatty alcohols comprising from 1 to 200 ethylene oxide groups, preferably from 1 to 50 ethylene oxide groups.

Preferably, the lightening composition used in the process according to the invention comprises one or more ethoxylated _C8 - _C24 fatty alcohols comprising from 1 to 200 ethylene oxide groups, preferably from 1 to 50 ethylene oxide groups.

When they are present, the surfactant(s) other than fatty acids are preferably present in the lightening composition used in the process according to the invention in a total content ranging from 0.01 to 20% by weight, more preferably from 0.1 to 15% by weight, better still from 0.5 to 10% by weight relative to the total weight of the composition which contains them.

When present, the non-ionic and/or anionic surfactant(s) other than fatty acids are preferably present in the composition(s) according to the invention in a total content ranging from 0.1 to 20% by weight, more preferably from 0.5 to 15% by weight, better still from 1 to 12% by weight relative to the total weight of the composition which contains them.

When present, the non-ionic surfactant(s) are preferably present in the composition(s) according to the invention in a total content ranging from 0.1 to 20% by weight, more preferably from 0.5 to 15% by weight, better still from 1 to 12% by weight relative to the total weight of the composition which contains them.

Organic solvent

The lightening composition used in the process according to the invention may comprise one or more organic solvent(s).

Preferably, the lightening composition used in the process according to the invention comprises one or more organic solvent(s).

Examples of organic solvents that may be mentioned include linear or branched C ₂ to C ₄ alkanols, such as ethanol and isopropanol; polyols and polyol ethers such as glycerol, 2-butoxyethanol, propylene glycol, dipropylene glycol, propane-1,3-diol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether, as well as aromatic alcohols or ethers such as benzyl alcohol or phenoxyethanol, and mixtures thereof.

When present, the organic solvent(s) are preferably present in the lightening composition in a total content ranging from 0.01 to 30% by weight, preferably ranging from 0.05 to 15% by weight, preferentially from 0.1 to 10% by weight relative to the total weight of the lightening composition.

The lightening composition is preferably an aqueous composition. In particular, it comprises more than 10% by weight of water, preferably more than 30% by weight of water, and even more advantageously more than 50% by weight of water. Preferably, the lightening composition comprises water in a content ranging from 10% to 95% by weight, preferably from 30% to 90% by weight, better still from 50 to 85% by weight relative to the total weight of the lightening composition.

Preferably, the pH of the lightening composition used in the process of the invention is between 8 and 13, preferably between 9 and 12.

The lightening composition according to the invention may optionally comprise one or more additives, among which may be mentioned anionic, non-ionic, amphoteric, cationic polymers or their mixtures, mineral thickening agents, anti-dandruff agents, anti-seborrheic agents, anti-hair loss and/or regrowth agents, vitamins and pro-vitamins including panthenol, sun filters, mineral or organic pigments, plasticizing agents, solubilizing agents, opacifying or pearlescent agents, antioxidant agents, sequestering agents, perfumes, preservatives.

Of course, those skilled in the art will take care to choose this or these possible complementary compounds in such a way that the advantageous properties intrinsically attached to the lightening composition are not, or not substantially, altered by the addition(s) envisaged.

The above additives may generally be present in an amount of between 0 and 20% by weight for each of them, relative to the total weight of the lightening composition.

Preferably, the lightening composition which has just been described is obtained at the time of use, by mixing an oxidizing composition comprising the chemical oxidizing agent(s) with an alkaline composition comprising the alkaline agent(s).

Oxidizing composition

In addition to the chemical oxidizing agent(s), the oxidizing composition may comprise one or more fatty substances as defined previously, preferably chosen from fatty alcohols, one or more surfactants as defined previously, preferably chosen from non-ionic surfactants, one or more solvent(s) as defined previously.

The oxidizing composition also preferably comprises one or more acidifying agents. Among the acidifying agents, mention may be made, for example, of mineral or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid, lactic acid, sulfonic acids.

The oxidizing composition is preferably an aqueous composition. In particular, it comprises more than 10% by weight of water, preferably more than 30% by weight of water, and even more advantageously more than 50% by weight of water. Preferably, the oxidizing composition comprises water in a content ranging from 10% to 95% by weight, preferably from 30% to 93% by weight, better still from 50 to 92% by weight relative to the total weight of the oxidizing composition.

The pH of the oxidizing composition is preferably less than 7, preferably between 1 and 5, preferentially between 1.5 and 4.5. This pH can be adjusted to the desired value by the use of one or more acidifying agents, which can in particular be chosen from those described above.

Alkaline composition

In addition to the alkaline agent(s) described above, the alkaline composition may comprise one or more fatty acids as defined above, one or more fatty substances as defined above, preferably chosen from solid fatty alcohols, solid esters of fatty acids and/or fatty alcohols and their mixtures, one or more surfactants as defined above, preferably chosen from non-ionic surfactants, one or more solvent(s) as defined above.

The alkaline composition is preferably an aqueous composition. In particular, it comprises water in a content ranging from 5% to 80% by weight, preferably from 10% to 70% by weight, better still from 20 to 50% by weight relative to the total weight of the alkaline composition.

The pH of the alkaline composition, when aqueous, preferably ranges from 8 to 12, preferably from 9 to 11, better still from 10 to 11.

Coloring composition Direct dyes

The coloring composition used in the process of the invention comprises one or more direct dye(s).

By "direct dye" we mean colored species. These are dyes that will diffuse superficially on the fiber.

The direct dye(s) that can be used according to the invention are chosen from natural direct dyes, synthetic direct dyes, and mixtures thereof.

Preferably, the direct dye(s) that can be used according to the invention are chosen from ionic direct dyes and non-ionic direct dyes, more particularly from cationic direct dyes, amphoteric direct dyes, anionic direct dyes, non-ionic direct dyes, and mixtures thereof.

The direct dyes are, for example, chosen from nitrobenzene direct dyes, azo direct dyes, tetraazapentamethine dyes, quinone and in particular anthraquinone dyes, azine direct dyes, triarylmethane direct dyes, azomethine direct dyes and natural direct dyes.

The coloring composition may comprise one or more non-ionic direct dyes.

Among the non-ionic direct dyes, we can cite neutral nitro benzene direct dyes, neutral azo direct dyes, neutral anthraquinone dyes.

The coloring composition may comprise one or more cationic direct dyes.

The term "cationic direct dye" means any dye other than oxidation dyes, commonly called "basic" direct dyes or "basic dyes". They are called basic because of their affinity with acidic substances, including in their structure at least one endo- or exocyclic cationic or cationizable group.

The cationic direct dye(s) contain at least one quaternized cationic chromophore or at least one chromophore carrying a quaternized or quaternizable cationic group.

According to a particular embodiment of the invention, the cationic direct dyes comprise at least one quaternized cationic chromophore.

As cationic direct dyes according to the invention, mention may be made of acridine dyes; acridones; anthranthrones; anthrapyrimidines; anthraquinones; azines; (poly)azo dyes, hydrazono or hydrazones, in particular arylhydrazones; azomethines; benzanthrones; benzimidazoles; benzimidazolones; benzindoles; benzoxazoles; benzopyrans; benzothiazoles; benzoquinones; bisazines; bisisoindolines; carboxanilides; coumarins; cyanines such as azacarbocyanines, diazacarbocyanines, diazahemicyanines, hemicyanines, or tetraazacarbocyanines; diazines; diketopyrrolopyrroles; dioxazines; diphenylamines; diphenylmethanes; dithiazines; flavonoids such as flavanthrones and flavones; fluorindines; formazans; indamines; indanthrones; indigoids and pseudo-indigoids; indophenols; indoanilines; isoindolines; isoindolinones; isoviolanthrones; lactones; (poly)methines such as stilbene or styryl dimethines; naphthalimides; naphthanilides; naphtholactams; naphthoquinones; nitro, including nitro(hetero)aromatics; oxadiazoles; oxazines; perilones; perinones; perylenes; phenazines; phenoxazine; phenothiazines; phthalocyanine; polyenes/carotenoids; porphyrins; pyranthrones; pyrazolanthrones; pyrazolones; pyrimidinoanthrones; pyronines; quinacridones; quinolines; quinophthalones; squaranes; tetrazoliums; thiazines, thioindigo; thiopyronines; triarylmethanes, or xanthenes.

For cationic azo dyes, we can particularly mention those derived from the cationic dyes described in the Kirk-Othmer Encyclopedia of Chemical Technology, “Dyes, Azo”, J. Wiley & Sons, updated on 04/19/2010.

Among the azo dyes that can be used according to the invention, mention may be made of the cationic azo dyes described in patent applications WO 95/15144, WO 95/01772 and EP 714954.

Among the azo dyes described in the Colour Index International 3rd edition, the following compounds may be mentioned:
-Basic Red 22
-Basic Red 76
-Basic Yellow 57
-Basic Brown 16
-Basic Brown 17.

Among the cationic quinone dyes, those mentioned in the aforementioned Colour Index International are suitable, and among these, the following dyes may be mentioned, among others:
-Basic Blue 22
-Basic Blue 99.

Suitable azine dyes include those listed in the Colour Index International, for example:
-Basic Blue 17
-Basic Red 2.

Among the cationic triarylmethane dyes which can be used according to the invention, mention may be made, in addition to those listed in the Colour Index, of the following dyes:
-Basic Green 1
-Basic Violet 3
-Basic Violet 14
-Basic Blue 7
-Basic Blue 26.

Cationic dyes can also be cited in documents US 5888252, EP 1133975, WO 03/029359, EP 860636, WO 95/01772, WO 95/15144, EP 714954. Those listed in the encyclopedia "The chemistry of synthetic dye" by K. VENKATARAMAN, 1952, Academic press vol 1 to 7, in the encyclopedia "Kirk-Othmer" "Chemical technology", chapter "Dyes and Dye intermediate", 1993, Wiley and sons, and in various chapters of the encyclopedia "ULLMANN's ENCYCLOPEDIA of Industrial chemistry" 7th edition, Wiley and sons.

Preferably, the cationic direct dyes are chosen from those derived from azo and hydrazono type dyes.

According to a particular embodiment, the direct dyes are cationic azo dyes, described in EP 850636, FR 2788433, EP 920856, WO 9948465, FR 2757385, EP 850637, EP 918053, WO 9744004, FR 2570946, FR 2285851, DE 2538363, FR 2189006, FR 1560664, FR 1540423, FR 1567219, FR 1516943, FR 1221122, DE 4220388, DE 4137005, WO 0166646, US 5708151, WO 9501772, WO 515144, GB 1195386, US 3524842, US 5879413, EP 1062940, EP 1133976, GB 738585, DE 2527638, FR 2275462, GB 1974-27645, Acta Histochem. (1978), 61(1), 48-52; Tsitologiya (1968), 10(3), 403-5; Zh. Obshch. Khim. (1970), 40(1), 195-202; Ann. Chem. (Rome) (1975), 65(5-6), 305-14; Journal of the Chinese Chemical Society (Taipei) (1998), 45(1), 209-211; Rev. Rum. Chem. (1988), 33(4), 377-83; Text. Res. J. (1984), 54(2), 105-7; Chem. Ind. (Milan) (1974), 56(9), 600-3; Khim. Tekhnol. (1979), 22(5), 548-53; Ger. Monatsh. Chem. (1975), 106(3), 643-8; MRL Bull. Res. Dev. (1992), 6(2), 21-7; Lihua Jianyan, Huaxue Fence (1993), 29(4), 233-4; Dyes Pigm. (1992), 19(1), 69-79; Dyes Pigm. (1989), 11(3), 163-72.

Preferably, the cationic direct dye(s) comprise a quaternary ammonium group, more preferably the cationic charge is endocyclic.

These cationic radicals are for example a cationic radical:
- with an exocyclic charge (di/tri)(C ₁ -C ₈ )alkylammonium, or
- with an endocyclic charge such as comprising a cationic heteroaryl group chosen from: acridinium, benzimidazolium, benzobistriazolium, benzopyrazolium, benzopyridazinium, benzoquinolium, benzothiazolium, benzotriazolium, benzoxazolium, bi-pyridinium, bis-tetrazolium, dihydrothiazolium, imidazopyridinium, imidazolium, indolium, isoquinolium, naphthoimidazolium, naphthooxazolium, naphthopyrazolium, oxadiazolium, oxazolium, oxazolopyridinium, oxonium, phenazinium, phenooxazolium, pyrazinium, pyrazolium, pyrazoyltriazolium, pyridinium, pyridinoimidazolium, pyrrolium, pyrylium, quinolium, tetrazolium, thiadiazolium, thiazolium, thiazolopyridinium, thiazoylimidazolium, thiopyrylium, triazolium or xanthylium.

Mention may be made of cationic hydrazono dyes of formula (C-II) and (C-III), azo dyes of the following formulas (C-IV) and (C-V), as well as their optical, geometric, tautomeric isomers, their salts of acids or bases, organic or mineral, as well as their solvates such as hydrates:

Hét ⁺ -C(Ra)=NN(Rb)-Ar, Q ^- (C-II)

Hét ⁺ -N(Ra)-N=C(Rb)-Ar, Q ^- (C-III)

Het ⁺ -N=N-Ar, Q ^- (C-IV)

Ar ⁺ -N=N-Ar'', Q ^- (CV),

formulas (C-II) to (CV) in which:
* Het ⁺ represents a cationic heteroaryl radical, preferably with an endocyclic cationic charge such as imidazolium, indolium, or pyridinium, optionally substituted preferentially by at least one (C ₁ -C ₈ )alkyl group such as methyl;
* Ar ⁺ represents an aryl radical, such as phenyl or naphthyl, with an exocyclic cationic charge, preferably ammonium, particularly tri(C ₁ -C ₈ )alkyl-ammonium such as trimethylammonium;
* Ar represents an aryl group, in particular phenyl, optionally substituted, preferably by one or more electron-donating groups such as i) (C ₁ -C ₈ )alkyl optionally substituted, ii) (C ₁ -C ₈ )alkoxy optionally substituted, iii) (di)(C ₁ -C ₈ )(alkyl)amino optionally substituted on the alkyl group(s) by a hydroxyl group, iv) aryl(C ₁ -C ₈ )alkylamino, v) N-(C ₁ -C ₈ )alkyl-N-aryl(C ₁ -C ₈ )alkylamino optionally substituted or Ar represents a julolidine group;
* Ar'' represents an optionally substituted (hetero)aryl group such as phenyl or pyrazolyl optionally substituted, preferably by one or more (C ₁ -C ₈ )alkyl, hydroxyl, (di)(C ₁ -C ₈ )(alkyl)amino, (C ₁ -C ₈ )alkoxy or phenyl groups;
* Ra and Rb, identical or different, representing a hydrogen atom or a (C ₁ -C ₈ )alkyl group optionally substituted, preferably by a hydroxyl group;
* or the substituent Ra with a substituent of Het+ and/or Rb with a substituent of Ar form together with the atoms which carry them a (hetero)cycloalkyl; particularly Ra and Rb, representing a hydrogen atom or a (C ₁ -C ₄ )alkyl group optionally substituted by a hydroxyl group;
* Q ^- represents an organic or inorganic anionic counterion such as a halide or an alkyl sulfate.

In particular, mention may be made of direct dyes with endocyclic azo and hydrazono cationic charges of formula (C-II) to (C-V) as defined above; more particularly the cationic direct dyes of formula (C-II) to (C-V) with endocyclic cationic charges described in patent applications WO 95/15144, WO 95/01772 and EP-714954.

Preferably, the following direct dyes can be mentioned:
(C-II-1),
(C-IV-1),

formulas (C-II-1) and (C-IV-1) in which:
- R ¹ represents a (C ₁ -C ₄ )alkyl group such as methyl;
- R ² and R ³ , identical or different, represent a hydrogen atom or a (C ₁ -C ₄ )alkyl group such as methyl; and
- R ⁴ represents a hydrogen atom or an electron-donating group such as (C ₁ -C ₈ )alkyl optionally substituted, (C ₁ -C ₈ )alkoxy optionally substituted, (di)(C ₁ -C ₈ )(alkyl)amino optionally substituted on the alkyl group(s) by a hydroxyl group; particularly R ⁴ is a hydrogen atom,
- Z represents a CH group or a nitrogen atom, preferably CH,
- Q ^- is an anionic counterion as defined above particularly halide such as chloride or an alkyl sulfate such as methyl sulfate or mesyl.

In particular, the dyes of formula (C-II-1) and (C-IV-1) are chosen from Basic Red 51, Basic Yellow 87 and Basic Orange 31 or their derivatives:
Basic Red 51
Basic Orange 31
Basic Yellow 87,

with Q’ an anionic counterion as defined above, particularly halide such as chloride or an alkyl sulfate such as methyl sulfate or mesyl.

According to a particular embodiment of the invention, the direct dyes are fluorescent, that is to say they contain at least one fluorescent chromophore as defined previously.

Examples of fluorescent dyes include radicals derived from acridines, acridones, benzanthrones, benzimidazoles, benzimidazolones, benzindoles, benzoxazoles, benzopyrans, benzothiazoles, coumarins, difluoro{2-[(2H-pyrrol-2-ylidene-kN)methyl]-1H-pyrrolato-kN}borons (BODIPY®), diketopyrrolo-pyrroles, fluorindines, (poly)methines (including cyanines and styryls/hemicyanines), naphthalimides, naphthanilides, naphthylamine (such as dansyls), oxadiazoles, oxazines, perilones, perinones, perylenes, polyenes/carotenoids, squaranes, stilbenes, xanthenes.

We can also cite the fluorescent dyes described in documents EP 1133975, WO 03/029359, EP 860636, WO 95/01772, WO 95/15144, EP 714954 and those listed in the encyclopedia "The chemistry of synthetic dye" by K. VENKATARAMAN, 1952, Academic press vol 1 to 7, in the encyclopedia "Kirk-Othmer" "Chemical technology", chapter "Dyes and Dye intermediate", 1993, Wiley and sons, and in various chapters of the encyclopedia "ULLMANN's ENCYCLOPEDIA of Industrial chemistry" 7th edition, Wiley and sons, in The Handbook — A Guide to Fluorescent Probes and Labeling Technologies, 10th Ed Molecular Probes/Invitrogen – Oregon 2005 distributed via the Internet or in previous printed editions.

According to a variant of the invention, the cationic dye(s) are fluorescent and comprise at least one quaternary ammonium radical such as those of the following formula (C-VI), as well as their optical, geometric, tautomeric isomers, their salts of acids or bases, organic or mineral, as well as their solvates such as hydrates:

W ⁺ –[C(Rc)=C(Rd)]m'–Ar, Q ^- (C-VI),

formula (C-VI) in which:
* W ⁺ represents a cationic heterocyclic or heteroaryl group, particularly comprising a quaternary ammonium optionally substituted by one or more (C ₁ -C ₈ )alkyl groups optionally substituted in particular by one or more hydroxyl groups;
* Ar representing an aryl group such as phenyl or naphthyl, optionally substituted preferentially by i) one or more halogen atoms, such as chlorine, fluorine; ii) one or more (C ₁ -C ₈ )alkyl groups, preferably C ₁ -C ₄ such as methyl; iii) one or more hydroxyl groups; iv) one or more (C ₁ -C ₈ )alkoxy groups such as methoxy; v) one or more hydroxy(C ₁ -C ₈ )alkyl groups such as hydroxyethyl, vi) one or more amino or (di)(C ₁ -C ₈ )alkylamino groups, preferably with the C ₁ -C ₄ alkyl part optionally substituted by one or more hydroxyl such as (di)hydroxyethylamino, vii) by one or more acylamino groups; (viii) one or more heterocycloalkyl groups such as piperazinyl, piperidinyl or 5 or 6 membered heteroaryl groups such as pyrrolidinyl, pyridinyl and imidazolinyl;
* m' represents an integer between 1 and 4 inclusive, particularly m is 1 or 2; more preferably 1;
* Rc, Rd, identical or different, represent a hydrogen atom or an optionally substituted (C ₁ -C ₈ )alkyl group, preferably C ₁ -C ₄ , or Rc contiguous to W ⁺ and/or Rd contiguous to Ar form with the atoms which carry them a (hetero)cycloalkyl, particularly Rc is contiguous to W ⁺ and form a (hetero)cycloalkyl such as cyclohexyl;
* Q ^- is an organic or inorganic anionic counterion as defined previously.

Among the cationic direct dyes, we can also mention the triarylmethane cationic dyes.

Preferably, the triarylmethane cationic direct dye(s) according to the invention are chosen from the cationic dyes of the following formulae (C-VII) and (C-VII'):
(C-VII),
(C-VII'),

as well as its addition salts with an acid or a base, organic or mineral, its geometric, optical, tautomeric isomers, and its mesomeric forms, its solvates such as hydrates,

formulas (C-VII) and (C-VII') above in which:
* R ₁ , R ₂ , R ₃ and R ₄ , identical or different, represent a hydrogen atom or a (C ₁ -C ₆ )alkyl group optionally substituted, preferably by a hydroxy group; aryl such as phenyl, aryl(C ₁ -C ₄ )alkyl such as benzyl, heteroaryl, heteroaryl(C ₁ -C ₄ )alkyl, or two groups R ₁ and R ₂ , and/or R ₃ and R ₄ , carried by the same nitrogen atom, form together with the nitrogen atom which carries them an optionally substituted heterocycloalkyl group such as morpholino, piparazino, piperidino, preferably R ₁ , R ₂ , R ₃ and R ₄ , identical or different, represent a hydrogen atom or a (C ₁ -C ₄ )alkyl group,
* R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ , identical or different, represent a hydrogen atom, a halogen atom, or a group chosen from i) hydroxy, ii) thiol, iii) amino iv) (di)(C ₁ -C ₄ )(alkyl)amino, v) (di)arylamino such as (di)phenylamino, vi) nitro, vii) acylamino (-NR-C(O)R') in which the radical R is a hydrogen atom, a C ₁ -C ₄ alkyl radical optionally carrying at least one hydroxyl group and the radical R' is a C ₁ -C ₂ alkyl radical; viii) carbamoyl ((R) ₂ NC(O)-) in which the radicals R, which may be identical or not, represent a hydrogen atom, a C ₁ -C ₄ alkyl radical optionally carrying at least one hydroxyl group; ix) carboxylic acid or ester, (-OC(O)R') or

(-C(O)OR'), in which the radical R' is a hydrogen atom, or C ₁ -C ₄ alkyl optionally carrying at least one hydroxyl group and the radical R' is a C ₁ -C ₂ alkyl radical; x) alkyl optionally substituted in particular by a hydroxy group; xi) alkylsulfonylamino (R'SO ₂ -NR-) in which the radical R represents a hydrogen atom, a C ₁ -C ₄ alkyl radical optionally carrying at least one hydroxyl group and the radical R' represents a C ₁ -C ₄ alkyl radical, a phenyl radical; xii) aminosulfonyl ((R) ₂ N-SO ₂ ^- ) in which the radicals R, which may or may not be identical, represent a hydrogen atom, a C ₁ -C ₄ alkyl radical optionally carrying at least one hydroxyl group, xiii) (C ₁ -C ₄ )alkoxy, and xiv) (C ₁ -C ₄ )alkylthio;
* Or two radicals carried by two contiguous carbon atoms R ₅ and R ₆ and/or R ₇ and R ₈ , and/or R ₉ and R ₁₀ and/or R ₁₁ and R ₁₂ and/or R ₁₃ and R ₁₄ and/or R ₁₅ and R ₁₆ form together with the carbon atoms which carry them a condensed 6-membered aryl or heteroaryl ring, preferably benzo, said ring possibly being further optionally substituted, preferably an unsubstituted benzo ring;
* Q ^- represents an anionic counterion to achieve electroneutrality, preferably selected from halides such as chloride, bromide, and phosphate.

When the cationic dye comprises one or more anionic substituents such as COOR or SO ₃ R with R denoting a hydrogen or a cation, it is understood that there are then more cationic substituents than anionic substituents, so that the overall resulting charge of the triarylmethane structure is cationic.

According to a preferred embodiment, the triarylmethane dye(s) is/are chosen from those of formula (C-VII) or (C-VII'), in which, taken together or separately,
- R ₁ , R ₂ , R ₃ and R ₄ represent a hydrogen atom or a (C ₁ -C ₄ )alkyl group such as methyl or ethyl,
- R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ , represent a hydrogen atom, halogen, such as chlorine, or a (C ₁ -C ₄ )alkyl group such as methyl or ethyl, an amino group, a (di)(C ₁ -C ₄ )(alkyl)amino group and, preferably, at least one of the groups R ₉ , R ₁₀ , R ₁₁ or R ₁₂ represents a hydrogen atom, halogen (Cl), or an amino group, or a (C ₁ -C ₄ )(alkyl)amino or (di)(C ₁ -C ₄ )(alkyl)amino group, preferably in the para position of the phenyl group.

Preferably, the direct dye(s) of triarylmethane structure are chosen from Basic Violet 1, Basic Violet 2, Basic Violet 3, Basic Violet 4, Basic Violet 14, Basic Blue 1, Basic Blue 7, Basic Blue 26, Basic green 1, Basic Blue 77 (also called HC Blue 15), and mixtures thereof.

Among the cationic direct dyes, we can also mention anthraquinone cationic dyes.

The anthraquinone cationic direct dye(s) that can be used in the coloring composition of the invention comprise a quaternary ammonium group.

These cationic radicals are for example a cationic radical:
- with exocyclic charge (C ₁ -C ₈ )alkylammonium, or
- with an endocyclic charge such as comprising a cationic heteroaryl group chosen from: acridinium, benzimidazolium, benzobistriazolium, benzopyrazolium, benzopyridazinium, benzoquinolium, benzothiazolium, benzotriazolium, benzoxazolium, bi-pyridinium, bis-tetrazolium, dihydrothiazolium, imidazopyridinium, imidazolium, indolium, isoquinolium, naphthoimidazolium, naphthooxazolium, naphthopyrazolium, oxadiazolium, oxazolium, oxazolopyridinium, oxonium, phenazinium, phenooxazolium, pyrazinium, pyrazolium, pyrazoyltriazolium, pyridinium, pyridinoimidazolium, pyrrolium, pyrylium, quinolium, tetrazolium, thiadiazolium, thiazolium, thiazolopyridinium, thiazoylimidazolium, thiopyrylium, triazolium or xanthylium.

Preferably, the cationic charge is exocyclic.

Among the anthraquinone cationic direct dyes, those of formula (C-VIII) having an exocyclic cationic charge are preferred:
(C-VIII)

in which:
- R ¹ , R ² and R ³ , identical or different, representing a hydrogen atom or an optionally substituted (C ₁ -C ₈ )alkyl group;
- R ⁴ representing a hydrogen atom or an optionally substituted (C ₁ -C ₈ )alkyl group;
- R ⁵ representing a hydrogen atom, an optionally substituted (C ₁ -C ₈ )alkyl group, an optionally substituted (C ₁ -C ₈ )alkylene group, a halogen, a hydroxyl group or a (C ₁ -C ₈ )alkoxy group
- n representing a number between 1 and 8;
- Q ^- represents an organic or inorganic anionic counterion such as a halide or an alkyl sulfate.

Preferably, in formula (C-VIII):
- R ¹ , R ² and R ³ , identical or different, representing an optionally substituted (C ₁ -C ₆ )alkyl group;
- R ⁴ representing a hydrogen atom or optionally substituted (C ₁ -C ₆ )alkyl group;
- R ⁵ representing a hydrogen atom or an optionally substituted (C ₁ -C ₈ )alkyl group,
- n representing a number between 1 and 6;
- Q ^- representing a halide or an alkyl sulfate.

More preferably, in formula (CVIII):
- R ¹ , R ² and R ³ , identical or different, representing an optionally substituted (C ₁ -C ₃ )alkyl group;
- R ⁴ representing a hydrogen atom or a methyl; preferably a methyl
- R ⁵ representing a hydrogen atom or a methyl, preferably a hydrogen atom;
- n representing a number between 2 and 4;
- Q ^- representing a halide or an alkyl sulfate, preferably a halide.

Among the dyes of formula (C-VIII), it is possible in particular to use the dyes of formula (C-VIII') or of formula (C-VIII'') following:
(C-VIII')
(C-VIII'')

with Q ^- an anionic counterion, particularly halide such as bromide or chloride, or an alkyl sulfate such as methyl sulfate or mesyl. Preferably Q ^- is a halide, more preferably a bromide.

By "anionic counterion" is meant an anion or an anionic group derived from an organic or mineral acid salt counterbalancing the cationic charge of the dye; more particularly the anionic counterion is chosen from i) halides such as chloride, bromide; ii) nitrates; iii) sulfonates including C ₁ -C ₆ alkylsulfonates: Alk-S(O) ₂ O- such as methylsulfonate or mesylate and ethylsulfonate; iv) arylsulfonates: Ar-S(O) ₂ O- such as benzenesulfonate and toluenesulfonate or tosylate; v) citrate; vi) succinate; vii) tartrate; viii) lactate; ix) alkylsulfates: Alk-OS(O)O- such as methylsulfate and ethylsulfate; x) aryl sulfates: Ar-OS(O)O- such as benzenesulfate and toluenesulfate; xi) alkoxy sulfates: Alk-OS(O) ₂ O- such as methoxy sulfate and ethoxy sulfate; xii) aryloxy sulfates: Ar-OS(O) ₂ O-, xiii) phosphates O=P(OH) ₂ -O-, O=P(O-) ₂ -OH O=P(O-) ₃ , HO-[P(O)(O-)]wP(O)(O-) ₂ with w being an integer; xiv) acetate; xv) triflate; and xvi) borates such as tetrafluoroborate, xvii) disulfate (O=) ₂ S(O-) ₂ or SO ₄ ^2- and monosulfate HSO ₄ ^- .

A particularly preferred dye of formula (C-VIII’) is HC Blue 17.

A particularly preferred dye of formula (C-VIII’’) is HC Blue 16 (1-methylamino-4-(3'-dimethylpropylammoniumpropylamino) antraquinone bromide).

Preferably, the anthraquinone cationic direct dye(s) are chosen from dyes of formula (C-VIII’) and (C-VIII’’), and more preferably from dyes of formula (C-VIII’’), better still from HC Blue 16.

The coloring composition according to the invention may comprise one or more anionic direct dyes.

The anionic direct dyes of the invention are dyes commonly called "acid" direct dyes for their affinity with alkaline substances. Anionic direct dyes are understood to mean any direct dye comprising in its structure at least one CO ₂ R or SO ₃ R substituent with R denoting a hydrogen atom or a cation originating from a metal or an amine, or an ammonium ion. The anionic dyes may be chosen from acid nitro direct dyes, acid azo dyes, acid azine dyes, acid triarylmethane dyes, acid indoamine dyes, acid anthraquinone dyes, acid indigoid dyes and acid natural dyes.

According to the invention, the anionic direct dye(s) may be chosen, alone or as a mixture, from the anionic direct dyes of formulae (A-II), (A-II'), (A-III), (A-III'), (A-IV), (A-IV'), (A-V), (A-V'), (A-VI), (A-VII), (A-VIII) and (A-IX) below:

(a) diaryl anionic azo dyes of formula (A-II) or (A-II'):
(A-II)
(A-II'),

formulas (A-II) and (A-II') in which:
* R ₇ , R ₈ , R ₉ , R ₁₀ , R' ₇ , R' ₈ , R' ₉ and R' ₁₀ , identical or different, represent a hydrogen atom or a group chosen from:
- alkyl;
- alkoxy, alkylthio;
- hydroxy, mercapto;
- nitro, nitroso;
- R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X''- with R° representing a hydrogen atom, an alkyl or aryl group; X, X' and X'', identical or different, representing an oxygen, sulfur or NR atom with R representing a hydrogen atom or an alkyl group;
- (O) ₂ S(O ^- )-, M ⁺ with M ⁺ representing a hydrogen atom or a cationic counterion;
- (O)CO ^- -, M ⁺ with M ⁺ as defined previously;
- R''-S(O) ₂ -, with R'' representing a hydrogen atom, an alkyl group, an aryl group, (di)(alkyl)amino, aryl(alkyl)amino; preferably a phenylamino or phenyl group;
- R'''-S(O) ₂ -X'- with R''' representing an alkyl group, optionally substituted aryl, X' as defined previously;
- (di)(alkyl)amino;
- aryl(alkyl)amino optionally substituted by one or more groups chosen from i) nitro; ii) nitroso; iii) (O)2S(O-)-, M ⁺ and iv) alkoxy with M ⁺ as defined previously;
- optionally substituted heteroaryl; preferably a benzothiazolyl group;
- cycloalkyl; in particular cyclohexyl,
- Ar ^- N=N ^- with Ar representing an optionally substituted aryl group; preferably a phenyl optionally substituted by one or more alkyl, (O) ₂ S(O ^- )-, M ⁺ or phenylamino groups;
- or two contiguous groups R ₇ with R ₈ or R ₈ with R ₉ or R ₉ with R ₁₀ together form a fused benzo group A'; and R' ₇ with R' ₈ or R' ₈ with R' ₉ or R' ₉ with R' ₁₀ together form a fused benzo group B'; with A' and B' optionally substituted by one or more groups chosen from i) nitro; ii) nitroso; iii) (O)2S(O-)-, M ⁺ ; iv) hydroxy; v) mercapto; vi) (di)(alkyl)amino; vii) R°-C(X)-X'-; viii) R°-X'-C(X)-; ix) R°-X'-C(X)-X''-; x) Ar-N=N- and xi) optionally substituted aryl(alkyl)amino; with M ⁺ , R°, X, X', X'' and Ar as defined previously;
* W represents a sigma s bond, an oxygen atom, a sulfur atom, or a divalent radical i) –NR- with R as defined above, or ii) methylene -C(Ra)(Rb)- with Ra and Rb, identical or different, representing a hydrogen atom or an aryl group, or Ra and Rb together form with the carbon atom which carries them a spiro cycloalkyl; preferentially W represents a sulfur atom or Ra and Rb together form a cyclohexyl;
it being understood that formulas (A-II) and (A-II') comprise at least one sulfonate radical (O) ₂ S(O ^- )-, M ⁺ or one carboxylate radical (O)CO ^- -, M ⁺ on one of the rings A, A', B, B' or C; preferably sodium sulfonate;

As an example of dyes of formula (A-II), we can cite: Acid Red 1, Acid Red 4, Acid Red 13, Acid Red 14, Acid Red 18, Acid Red 27, Acid Red 28, Acid Red 32, Acid Red 33, Acid Red 35, Acid Red 37, Acid Red 40, Acid Red 41, Acid Red 42, Acid Red 44, Pigment red 57, Acid Red 68, Acid Red 73, Acid Red 135, Acid Red 138, Acid Red 184, Food Red 1, Food Red 13, Acid Orange 6, Acid Orange 7, Acid Orange 10, Acid Orange 19, Acid Orange 20, Acid Orange 24, Yellow 6, Acid Yellow 9, Acid Yellow 36, Acid Yellow 199, Food Yellow 3; Acid Violet 7, Acid Violet 14, Acid Blue 113, Acid Blue 117, Acid Black 1, Acid Brown 4, Acid Brown 20, Acid Black 26, Acid Black 52, Food Black 1, Food Black 2; Food yellow 3 or sunset yellow;

and as examples of dyes of formula (A-II’), we can cite: Acid Red 111, Acid Red 134, Acid yellow 38;

b) the azo anionic pyrrazolone dyes of formula (A-III) and (A-III'):

(A-III)
(A-III'),

formulas (A-III) and (A-III') in which:
* R ₁₁ , R ₁₂ and R ₁₃ , identical or different, represent a hydrogen atom, halogen atom, an alkyl group or -(O) ₂ S(O ^- ), M ⁺ with M ⁺ as defined previously;
* R ₁₄ represents a hydrogen atom, an alkyl group or a -C(O)O ^- group, M ⁺ with M ⁺ as defined previously;
* R ₁₅ represents a hydrogen atom;
* R ₁₆ represents an oxo group in which case R' ₁₆ is absent, or R ₁₅ with R ₁₆ together form a double bond;
* R ₁₇ and R ₁₈ , identical or different, represent a hydrogen atom, or a group chosen from:
- (O) ₂ S(O ^- )-, M ⁺ with M ⁺ as defined previously;
- Ar-OS(O) ₂ - with Ar representing an optionally substituted aryl group; preferably a phenyl optionally substituted by one or more alkyl groups;
* R ₁₉ and R ₂₀ together form either a double bond or a benzo D' group, optionally substituted;
* R' ₁₆ , R' ₁₉ and R' ₂₀ , identical or different, represent a hydrogen atom or an alkyl or hydroxy group;
* R ₂₁ represents a hydrogen atom, an alkyl group, or an alkoxy group;
* Ra and Rb, identical or different, are as defined previously, preferably Ra represents a hydrogen atom and Rb represents an aryl group;
* Y represents either a hydroxy group or an oxo group;
* represents a single bond when Y is an oxo group; and represents a double bond when Y represents a hydroxy group;
it being understood that formulas (A-III) and (A-III') comprise at least one sulfonate radical (O) ₂ S(O ^- )-, M ⁺ or one carboxylate radical -C(O)O-, M+ on one of rings D or E; preferably sodium sulfonate;
Examples of dyes of formula (A-III) include: Acid Red 195, Acid Yellow 23, Acid Yellow 27, Acid Yellow 76, and examples of dyes of formula (A-III') include: Acid Yellow 17;

c) the anthraquinone dyes of formula (A-IV) and (A-IV'):
(A-IV),
(A-IV')

formulas (A-IV) and (A-IV') in which:
* R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ , R ₂₆ and R ₂₇ , identical or different, represent a hydrogen atom, a halogen atom, or a group chosen from:
- alkyl;
- hydroxy, mercapto;
- alkoxy, alkylthio;
- optionally substituted aryloxy or arylthio, preferably substituted by one or more groups chosen from alkyl and (O) ₂ S(O ^- )-, M ⁺ with M ⁺ as defined previously;
- aryl(alkyl)amino optionally substituted by one or more groups chosen from alkyl and (O) ₂ S(O ^- )-, M ⁺ with M ⁺ as defined previously;
- (di)(alkyl)amino;
- (di)(hydroxyalkyl)amino
- (O) ₂ S(O ^- )-, M ⁺ with M ⁺ as defined previously;
* Z' represents a hydrogen atom or a group NR ₂₈ R ₂₉ with R ₂₈ and R ₂₉ , identical or different, representing a hydrogen atom or a group chosen from:
- alkyl;
- polyhydroxyalkyl such as hydroxyethyl;
- aryl optionally substituted by one or more groups, particularly i) alkyl such as methyl, n-dodecyl, n-butyl; ii) (O) ₂ S(O ^- )-, M+ with M ⁺ as defined above; iii) R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X''- with R°, X, X' and X'' as defined above, preferably R° represents an alkyl group;
- cycloalkyl; in particular cyclohexyl;
* Z, represents a group chosen from hydroxy and NR' ₂₈ R' ₂₉ with R' ₂₈ and R' ₂₉ , identical or different, representing the same atoms or groups as R ₂₈ and R ₂₉ as defined previously;
it being understood that formulas (A-IV) and (A-IV') comprise at least one sulfonate radical (O) ₂ S(O ^- )-, M ⁺ or one carboxylate radical -C(O)O ^- , M ⁺ ; preferably sodium sulfonate;
Examples of dyes of formula (A-IV) include: Acid Blue 25, Acid Blue 43, Acid Blue 62, Acid Blue 78, Acid Blue 129, Acid Blue 138, Acid Blue 140, Acid Blue 251, Acid Green 25, Acid Green 41, Acid Violet 42, Acid Violet 43, Mordant Red 3; EXT violet No. 2;
and as an example of dyes of formula (A-IV') we can cite: Acid Black 48;

(d) nitrated dyes of formula (AV), and (A-V'):
(AV)
(A-V')

formulas (AV) and (A-V') in which:
* R ₃₀ , R ₃₁ and R ₃₂ , identical or different, represent a hydrogen atom, a halogen atom, or a group chosen from:
- alkyl;
- alkoxy optionally substituted by one or more hydroxy groups, alkylthio optionally substituted by one or more hydroxy groups;
- hydroxy, mercapto;
- nitro, nitroso;
- polyhaloalkyl;
- R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X''- with R°; X, X' and X'' as defined previously;
- (O) ₂ S(O ^- )-, M ⁺ with M ⁺ as defined previously;
- (O)CO ^- -, M ⁺ with M ⁺ as defined previously;
- (di)(alkyl)amino;

- (di)(hydroxyalkyl)amino;
- heterocycloalkyl such as piperidino, piperazino or morpholino;
particularly R ₃₀ , R ₃₁ and R ₃₂ represent a hydrogen atom;
* Rc and Rd, identical or different, represent a hydrogen atom or an alkyl group;
* W is as defined previously; W particularly represents an –NH– group;
* ALK represents a divalent, linear or branched, C ₁ -C ₆ alkylene group; particularly ALK represents a –CH ₂ -CH ₂ - group;
* n is 1 or 2;
* p represents an integer between 1 and 5 inclusive;
* q represents an integer between 1 and 4 inclusive;
* u is 0 or 1;
* when n is 1, J represents a nitro, or nitroso group; particularly nitro;
* when n is 2, J represents an oxygen atom, a sulfur atom, or a divalent radical –S(O) _m – with m representing an integer 1 or 2; preferably J represents a radical –SO ₂ –;
* M' represents a hydrogen atom or a cationic counterion;
* present or absent represents a benzo group,
optionally substituted by one or more R ₃₀ groups as defined previously;
it being understood that the formulas (AV) and (A-V') comprise at least one sulfonate radical (O) ₂ S(O ^- )-, M ⁺ or one carboxylate radical -C(O)O-, M ⁺ ; preferably sodium sulfonate;

Examples of dyes of formula (A-V) include: Acid Brown 13; Acid Orange 3; examples of dyes of formula (A-V') include: Acid Yellow 1, 2,4-dinitro-1-naphthol-7-sulfonic acid sodium salt, 2-piperidino 5-nitro benzene sulfonic acid, 2(4'-N,N(2"-hydroxyethyl)amino-2'-nitro)aniline ethane sulfonic acid, 4-b-hydroxyethylamino-3-nitrobenzene sulfonic acid; EXT D&C yellow 7;

(e) triarylmethane dyes of formula (A-VI):
(A-VI)

formula (A-VI) in which:
* R ₃₃ , R ₃₄ , R ₃₅ and R ₃₆ , identical or different, represent a hydrogen atom or a group chosen from alkyl, optionally substituted aryl and optionally substituted arylalkyl; particularly an alkyl and benzyl group optionally substituted by a group (O) _m S(O ^- )-, M ⁺ with M ⁺ and m as defined previously;
* R ₃₇ , R ₃₈ , R ₃₉ , R ₄₀ , R ₄₁ , R ₄₂ , R ₄₃ and R ₄₄ , identical or different, represent a hydrogen atom or a group chosen from:
- alkyl;
- alkoxy, alkylthio;
- (di)(alkyl)amino;
- hydroxy, mercapto;
- nitro, nitroso;
- R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X''- with R° representing a hydrogen atom, an alkyl or aryl group; X, X' and X'', identical or different, representing an oxygen, sulfur or NR atom with R representing a hydrogen atom or an alkyl group;
- (O) ₂ S(O ^- )-, M ⁺ with M ⁺ representing a hydrogen atom or a cationic counterion;
- (O)CO ^- -, M ⁺ with M ⁺ as defined previously;
- or two contiguous groups R ₄₁ with R ₄₂ or R ₄₂ with R ₄₃ or R ₄₃ with R ₄₄ together form a fused benzo group: I'; with I' optionally substituted by one or more groups chosen from i) nitro; ii) nitroso; iii) (O) ₂ S(O ^- )-, M ⁺ ; iv) hydroxy; v) mercapto; vi) (di)(alkyl)amino; vii) R°-C(X)-X'-; viii) R°-X'-C(X)-; ix) R°-X'-C(X)-X''-; with M+, R°, X, X', X'' as defined above;
particularly R ₃₇ to R ₄₀ represent a hydrogen atom, and R ₄₁ to R ₄₄ , identical or different, represent a hydroxy group or (O) ₂ S(O ^- )-, M ⁺ ; and when R ₄₃ with R ₄₄ together form a benzo group, it is preferentially substituted by a (O) ₂ S(O ^- )- group;
it being understood that at least one of the cycles G, H, I or I' comprises at least one sulfonate radical (O) ₂ S(O ^- )- or one carboxylate radical -C(O)O ^- ; preferably sulfonate.
Examples of dyes of formula (A-VI) include: Acid Blue 1; Acid Blue 3; Acid Blue 7, Acid Blue 9; Acid Violet 49; Acid green 3; Acid green 5; Acid Green 50;

(f) xanthene-derived dyes of formula (A-VII):
(A-VII)

formula (A-VII) in which:
* R ₄₅ , R ₄₆ , R ₄₇ and R ₄₈ , identical or different, represent a hydrogen atom or a halogen atom;
* R ₄₉ , R ₅₀ , R ₅₁ and R ₅₂ , identical or different, represent a hydrogen atom, a halogen atom, or a group chosen from:
- alkyl;
- alkoxy, alkylthio;
- hydroxy, mercapto;
- nitro, nitroso;
- (O) ₂ S(O ^- )-, M ⁺ with M ⁺ representing a hydrogen atom or a cationic counterion;
- (O)CO ^- -, M ⁺ with M ⁺ as defined previously;
particularly R ₅₃ , R ₅₄ , R ₅₅ and R ₄₈ represent a hydrogen or halogen atom;
* G represents an oxygen atom, sulfur atom or an NR group with R representing a hydrogen atom or an alkyl group; particularly G represents an oxygen atom;
* L represents an alkoxide O ^-, M ⁺ ; a thioalcoholate S ^- , M ⁺ or an NRf group, with Rf representing a hydrogen atom or an alkyl group, and M ⁺ as defined previously; M ⁺ is particularly sodium or potassium;
* L' represents an oxygen atom, sulfur atom or an ammonium group: N ⁺ RfRg, with Rf and Rg, identical or different, representing a hydrogen atom, an alkyl group, an optionally substituted aryl group; L' particularly represents an oxygen atom or a phenylamino group optionally substituted by one or more alkyl groups or (O) _m S(O ^- )-, M ⁺ with m and M ⁺ as defined previously;
* Q and Q', identical or different, represent an oxygen or sulfur atom; particularly Q and Q' represent an oxygen atom;
* M ⁺ is as defined previously.

Examples of dyes of formula (A-VII) include: Acid Yellow 73; Acid Red 51; Acid Red 52, Acid Red 87; Acid Red 92; Acid Red 95; Acid Violet 9;

g) dyes derived from indole of formula (A-VIII):
(A-VIII),

formula (A-VIII) in which:
* R ₅₃ , R ₅₄ , R ₅₅ , R ₅₆ , R ₅₇ , R ₅₈ , R ₅₉ and R ₆₀ , identical or different, represent a hydrogen atom or a group chosen from:
- alkyl;
- alkoxy, alkylthio;
- hydroxy, mercapto;
- nitro, nitroso;

- R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X''- with R° representing a hydrogen atom, an alkyl or aryl group; X, X' and X'', identical or different, representing an oxygen, sulfur or NR atom with R representing a hydrogen atom or an alkyl group;
- (O) ₂ S(O ^- )-, M ⁺ with M ⁺ representing a hydrogen atom or a cationic counterion;
- (O)CO ^- -, M ⁺ with M ⁺ as defined previously;
* G represents an oxygen atom, sulfur atom or an NR group with R representing a hydrogen atom or an alkyl group; particularly G represents an oxygen atom;
* Ri and Rh, identical or different, represent a hydrogen atom or an alkyl group;
it being understood that formula (A-VIII) comprises at least one sulfonate radical (O) ₂ S(O ^- )-, M ⁺ or one carboxylate radical -C(O)O ^- , M ⁺ ; preferentially sodium sulfonate;

Examples of dyes of formula (A-VIII) include: Acid Blue 74.

(h) quinoline-derived dyes of formula (A-IX):
(A-IX),

formula (A-IX) in which:
* R ₆₁ represents a hydrogen atom, halogen or an alkyl group;
* R ₆₂ , R ₆₃ , and R ₆₄ , identical or different, represent a hydrogen atom or a group (O) ₂ S(O ^- )-, M ⁺ with M ⁺ representing a hydrogen atom or a cationic counterion;
* or R ₆₁ with R ₆₂ , or R ₆₁ with R ₆₄ , together form a benzo group optionally substituted by one or more (O) ₂ S(O ^- )-, M ⁺ groups with M ⁺ representing a hydrogen atom or a cationic counterion;
it being understood that formula (A-IX) comprises at least one sulfonate radical (O) ₂ S(O ^- )-, M ⁺ preferably sodium sulfonate.

Examples of dyes of formula (A-IX) include: Acid Yellow 2, Acid Yellow 3 and Acid Yellow 5.

More particularly, the coloring composition comprises one or more anionic direct dyes chosen, alone or as a mixture, from the following anionic direct dyes:

(C.I. 45380) Acid Red 87 (A-VII) (C.l. 10316) 2,4-Dinitro-1-naphthol-7-sulfonic acid sodium salt (A-V') (C.l. 10383) Acid Orange 3 (A-V) (C.l. 13015) Acid Yellow 9 / Food Yellow 2 (A-II) (C.l. 14780) / Direct Red 45 / Food Red 13 (A-II) (C.l. 13711) Acid Black 52 (A-II) (C.l. 13065) Acid Yellow 36 (A-II) (C.l. 14700) 1-Hydroxy-2-(2',4'-xylyl-5-sulfonatoazo)-naphthalene-4-sulfonic acid sodium salt / Food Red 1 (A-II) (C.l. 14720) Acid Red 14 / Food Red 3 / Mordant Blue 79 (A-II) (C. l. 14805) 4-Hydroxy-3-[(2-methoxy-5-nitrophenyl)diaza]-6-(phenylamino)naphthalene-2-sulfonic acid sodium salt / Acid Brown 4 (A-II) (C.l. 15510) Acid Orange 7 / Pigment Orange 17 / Solvent Orange 49 (A-II) (C.l. 15985) Food Yellow 3 / Pigment Yellow 104 (A-II) (C.l. 16185) Acid Red 27 / Food Red 9 (A-II) (C.l. 16230) Acid Orange 10 / Food Orange 4 (A-II) (C.l. 16250) Acid Red 44 (A-II) (C.l. 17200) Acid Red 33 / Food Red 12 (A-II) (C.l. 15685) Acid Red 184 (A-II) (C.l. 19125) Acid Violet 3 (A-II) (C.I. 18055) 1-Hydroxy-2-(4'-acetamidophenylazo)-8-acetamido-naphthalene-3,6-disulfonic acid sodium salt / Acid Violet 7 / Food Red 11 (A-II) (C.l. 18130) Acid Red 135 (A-II) (C.l. 19130) Acid Yellow 27(A-III) (C.l. 19140) Acid Yellow 23 / Food Yellow 4 (A-III) (C.l. 20170) 4'-(sulfonato-2'',4''-dimethyl)-bis-(2,6-phenylazo)-1,3-dihydroxy benzene / Acid Orange 24 (A-II) (C.l. 20470) 1-Amino-2-(4'-nitrophenylazo)-7-phenylazo-8-hydroxy-naphthalene-3,6-disulfonic acid sodium salt / Acid Black 1 (A-II) (C.l. 23266) (4-((4-methylphenyl)sulfonyloxy)-phenylazo)2,2'-dimethyl-4-((2-hydroxy-5,8-disulfonato)naphthylazo)biphenyl / Acid Red 111 (A-II’) (C.l. 27755) Food Black 2 (A-II) (C.l. 25440) 1-(4'-sulfonatophenylazo)-4-((2"-hydroxy-3"-acetylamino-6",8"-disulfonato)naphthylazo)-6-sulfonatonaphthalene (tetrasodium salt) / Food Black 1 (A-II) (C.I. 42090) Acid Blue 9 (A-VI) (C.I. 60730) Acid Violet 43 (A-IV) (C.I. 61570) Acid Green 25 (A-IV) (C.I. 62045) 1-Amino-4-cyclohexylamino-9,10-anthraquinone 2-sulfonic acid sodium salt / Acid Blue 62 (A-IV) (C.I. 62105) Acid Blue 78 (A-IV) (C.l. 14710) 4-Hydroxy-3((2-methoxyphenyl)-azo)-1-naphthalenesulfonic acid sodium salt / Acid Red 4 (A-II) 2-Piperidino 5-nitro benzene sulfonic acid (V’) 2(4'-N,N(2"-hydroxyethyl)amino-2'-nitro)aniline ethanesulfonic acid (A-V') 4-β-Hydroxyethylamino-3-nitrobenzene acid
Sulfonic acid (A-V') (C.I. 42640) Acid Violet 49 (A-VI) (C.I. 42080) Acid Blue 7 (A-VI) (C.I. 58005) 1,2-dihydroxy-3-sulfo-anthraquinone sodium salt / Mordant Red 3 (A-IV) (C.I. 62055) 1-Amino-9,10-dihydro-9,10-dioxo-4-(phenylamino) 2-anthracenesulfonic acid sodium salt / Acid Blue 25 (A-IV) (C.I. 14710) 4-Hydroxy-3-((2-methoxyphenyl)-azo)-1-naphthalenesulfonic acid sodium salt / Acid Red 4 (A-II)

Most of these dyes are described in particular in the Color Index published by The Society of Dyers and Colorists, P.O. Box 244, Perkin House, 82 Grattan Road, Bradford, Yorkshire, BD1 2JBN England.

More particularly preferred anionic dyes are the dyes designated in the Color Index under the code C.I. 58005 (monosodium salt of 1,2-dihydroxy-9,10-anthraquinone-3-sulfonic acid), C.I. 60730 (monosodium salt of 2-[(9,10-dihydro-4-hydroxy-9,10-dioxo-1-anthracenyl)-amino]-5-methyl-benzenesulfonic acid), C.I. 15510 (monosodium salt of 4-[(2-hydroxy-1-naphthalenyl)-azo]-benzenesulfonic acid), C.I. 15985 (disodium salt of 6-hydroxy-5-[(4-sulfophenyl)-azo]-2-naphthalenesulfonic acid), C.I. 17200 (disodium salt of 5-amino-4-hydroxy-3-(phenylazo)-2,7-naphthalene disulfonic acid), C.I. 20470 (1-amino-2-(4'-nitrophenylazo)-7-phenylazo-8-hydroxy-3,6-naphthalene disulfonic acid, disodium salt), C.I. 42090 (N-ethyl-N-[4-[[4-[ethyl[3-sulfophenyl)-methyl]-amino]-phenyl](2-sulfophenyl)-methylene]-2,5-cyclohexadien-1-ylidene]-3-sulfobenzenemethanaminium hydroxide, inner salt, disodium salt), C.I. 61570 (disodium salt of 2,2'-[(9,10-dihydro-9,10-dioxo-1,4-anthracenediyl)-diimino]-bis-[5-methyl]-benzenesulfonic acid.

Compounds corresponding to the mesomeric, tautomeric forms of structures (A-II) to (A-IX) can also be used.

Among the natural direct dyes that can be used according to the invention, mention may be made of hennotannic acid, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogallin, protocatechaldehyde, indigo, isatin, curcumin, spinulosin, apigenidin and orcein. Extracts or decoctions containing these natural dyes and in particular poultices or extracts based on henna may also be used.

Preferably, the coloring composition used in the process of the invention comprises one or more cationic direct dye(s).

More preferably, the coloring composition used in the process of the invention comprises one or more cationic direct dye(s) chosen from azo cationic direct dyes, hydrazono cationic direct dyes, anthraquinone cationic direct dyes, and mixtures thereof.

Advantageously, the total content of the direct dye(s) ranges from 0.001 to 20% by weight, preferably from 0.005 to 15% by weight, more preferably from 0.01 to 10% by weight, better still from 0.05 to 5% by weight, even better still from 0.1 to 3% by weight, relative to the total weight of the coloring composition.

Aromatic compound

The coloring composition used in the process of the invention comprises at least one compound of formula (I):
(I)

in which Y represents a C ₁ -C ₄ hydroxyalkyl group or a C ₁ -C ₄ hydroxyalkyloxy radical, n denotes an integer ranging from 0 to 5, X, identical or different, represents a C ₁ -C ₄ alkyl radical or a halogen. Preferably, n is equal to 0. According to a particular embodiment, Y represents a hydroxymethyl, hydroxyethyl or hydroxyethyloxy radical.

Examples of compounds of formula (I) include benzyl alcohol, phenyl ethanol, phenoxyethanol. According to a particular embodiment, the compound of formula (I) is benzyl alcohol.

According to a particular embodiment, the quantity of compounds of formula (I) varies from 0.01 to 10% by weight, preferably from 0.05 to 8% by weight, better still from 0.1 to 5% by weight, relative to the total weight of the coloring composition.

Aliphatic solvent

The coloring composition used in the process of the invention comprises at least one C ₂ -C ₆ hydroxylated aliphatic solvent.

Aliphatic means a compound not containing an aromatic nucleus. Solvents of this type may be monoalcohols or polyols that are liquid at room temperature (25°C) and atmospheric pressure (105 Pa). Preferably, these solvents are non-etherified. According to a particular embodiment, these solvents are chosen from ethanol, glycerol, propylene glycol, dipropylene glycol, hexylene glycol. Preferably, the C ₂ -C ₆ hydroxylated aliphatic solvent is ethanol and/or hexylene glycol, preferably ethanol.

According to one embodiment, the amount of hydroxylated aliphatic solvent varies from 0.1% to 40% by weight, preferably from 0.5 to 30% by weight, more preferably from 1 to 20% by weight, better still from 2 to 15% by weight, even better still from 3 to 10% by weight, relative to the weight of the coloring composition.

Preferably, the composition comprises benzyl alcohol and ethanol.

According to a particular embodiment, the weight ratio of compounds of formula (I)/C ₂ -C ₆ hydroxylated aliphatic solvent(s) is less than or equal to 1, preferably ranges from 0.1 to 1, better still from 0.1 to 0.5.

According to a particular embodiment, the weight ratio of benzyl alcohol/ethanol is less than or equal to 1, preferably ranging from 0.1 to 1, better still from 0.1 to 0.5.

Polysaccharide

The coloring composition used in the method of the invention may also comprise one or more polysaccharide(s).

In the present invention, the term "polysaccharide" means a polymer consisting of sugar units. The term "sugar unit" means an oxygenated hydrocarbon compound which has several alcohol functions, with or without aldehyde or ketone functions, and which comprises at least 4 carbon atoms. The sugar units may optionally be modified by substitution, and/or by oxidation and/or by dehydration.

The sugar units which may be included in the composition of the polysaccharides of the invention are preferably derived from the following sugars: glucose; galactose; arabinose; rhamnose; mannose; xylose; fucose; anhydrogalactose; galacturonic acid; glucuronic acid; mannuronic acid; galactose sulfate; anhydrogalactose sulfate and fructose.

Examples of polysaccharides include the following polymers, alone or in a mixture:
(a) exudates from trees or shrubs including:
- gum arabic (branched polymer of galactose, arabinose, rhamnose and glucuronic acid);
- gum ghatti (polymer derived from arabinose, galactose, mannose, xylose and glucuronic acid);
- karaya gum (polymer from galacturonic acid, galactose, rhamnose and glucuronic acid);
- gum tragacanth (or tragacanth) (polymer of galacturonic acid, galactose, fucose, xylose and arabinose);
b) gums derived from algae including:
- agar (polymer made from galactose and anhydrogalactose);
- alginates (polymers of mannuronic acid and glucuronic acid);
- carrageenans and furcellerans (polymers of galactose sulfate and anhydrogalactose sulfate);
(c) gums from seeds or tubers of which:
- guar gum (polymer of mannose and galactose);
- carob gum (polymer of mannose and galactose);
- fenugreek gum (polymer of mannose and galactose);
- tamarind gum (polymer of galactose, xylose and glucose);
- konjac gum (polymer of glucose and mannose);
(d) microbial gums including:
- xanthan gum (polymer of glucose, mannose acetate, mannose/pyruvic acid and glucuronic acid);
- gellan gum (polymer of partially acylated glucose, rhamnose and glucuronic acid);
- scleroglucan gum (glucose polymer);
(e) polymers extracted from plants including:
- celluloses (glucose polymers);
- starches (glucose polymers) and
- inulin.

These polymers can be modified physically or chemically. Physical treatments include heat treatment. Chemical treatments include esterification, etherification, amidation, and oxidation reactions. These treatments produce polymers that can be non-ionic, anionic, or amphoteric.

In particular, guar gums, locust bean gums, starches and celluloses can be modified/processed.

The guar gums that can be used according to the invention can be modified by C ₁ -C ₆ (poly)hydroxyalkyl groups. Among the C ₁ -C ₆ (poly)hydroxyalkyl groups, mention may be made, by way of example, of the hydroxymethyl, hydroxyethyl, hydroxypropyl and hydroxybutyl groups. These guar gums are well known in the state of the art and can, for example, be prepared by reacting corresponding alkene oxides such as, for example, propylene oxides with guar gum so as to obtain a guar gum modified by hydroxypropyl groups. The hydroxyalkylation rate preferably varies from 0.4 to 1.2 and corresponds to the number of alkylene oxide molecules consumed by the number of free hydroxyl functions present on the guar gum.

Such guar gums, possibly modified by hydroxyalkyl groups, are for example sold under the trade names JAGUAR HP8, JAGUAR HP60 and JAGUAR HP120 by the company RHODIA CHIMIE.

The starches that can be used in the present invention may be of botanical origin from cereals or tubers. Thus, the starches are, for example, chosen from corn, rice, oat, cassava, barley, potato, wheat, sorghum, pea, and tapioca starches. Hydrolysates of the starches mentioned above may also be used. The starch is preferably derived from potatoes.

Preferably, starch phosphates will be used, in particular distarch phosphates or compounds rich in distarch phosphate such as the product offered under the references PREJEL VA-70-T AGGL (gelatinized hydroxypropyl cassava distarch phosphate) or PREJEL TK1 (gelatinized cassava distarch phosphate) or PREJEL 200 (gelatinized acetylated cassava distarch phosphate) by the company AVEBE or STRUCTURE ZEA from NATIONAL STARCH (gelatinized corn distarch phosphate).

According to the invention, amphoteric starches can also be used, these amphoteric starches comprise one or more anionic groups and one or more cationic groups. The anionic and cationic groups can be linked to the same reactive site of the starch molecule or to different reactive sites; preferably they are linked to the same reactive site. The anionic groups can be of the carboxylic, phosphate or sulfate type and preferably carboxylic. The cationic groups can be of the primary, secondary, tertiary or quaternary amine type.

The polysaccharides that can be used according to the invention can be cellulose polymers.

According to the invention, the term "cellulosic" polymer means any polysaccharide compound having in its structure chains of glucose residues joined by β-1,4 bonds; in addition to unsubstituted celluloses, cellulose derivatives can be anionic, cationic, amphoteric or non-ionic.

Cellulosic polymers are also called celluloses.

Thus, the cellulose polymers which can be used according to the invention can be chosen from unsubstituted celluloses including in microcrystalline form and cellulose ethers.

Among these cellulose polymers, we distinguish cellulose ethers, cellulose esters and cellulose ether esters.

Cellulose esters include inorganic cellulose esters (cellulose nitrates, sulfates, or phosphates), organic cellulose esters (cellulose monoacetates, triacetates, amidopropionates, acetatebutyrates, acetatepropionates, or acetatetrimellitates), and mixed organic/inorganic cellulose esters such as cellulose acetatebutyrate sulfates and acetatepropionate sulfates. Cellulose ether esters include hydroxypropylmethylcellulose phthalates and ethylcellulose sulfates.

Examples of cellulose ethers include (C ₁ -C ₄ )alkylcelluloses such as methylcelluloses and ethylcelluloses (e.g., Ethocel Standard 100 Premium from DOW CHEMICAL); (poly)hydroxy(C ₁ -C ₄ )alkylcelluloses such as hydroxymethylcelluloses, hydroxyethylcelluloses (e.g., Natrosol 250 HHR offered by ASHLAND) and hydroxypropylcelluloses (e.g., Klucel EF from AQUALON); mixed celluloses (poly)hydroxy(C ₁ -C ₄ )alkyl-(C ₁ -C ₄ )alkylcelluloses such as hydroxypropylmethylcelluloses (e.g., Methocel E4M from DOW CHEMICAL), hydroxyethylmethylcelluloses, hydroxyethylethylcelluloses (e.g., Bermocoll E 481 FQ from AKZO NOBEL) and hydroxybutylmethylcelluloses.

Among the anionic cellulose ethers, mention may be made of (poly)carboxy(C ₁ -C ₄ )alkylcelluloses and their salts. For example, mention may be made of carboxymethylcelluloses, carboxymethylmethylcelluloses (for example Blanose 7M from the company AQUALON) and carboxymethylhydroxyethylcelluloses and their sodium salts.

Among the cationic cellulose ethers, mention may be made of cationic cellulose derivatives such as cellulose copolymers or cellulose derivatives grafted with a water-soluble quaternary ammonium monomer, and described in particular in patent US4131576, such as (poly)hydroxy( _C1 - _C4 )alkyl celluloses, such as hydroxymethyl-, hydroxyethyl- or hydroxypropyl celluloses grafted in particular with a salt of methacryloylethyltrimethylammonium, methacrylmidopropyltrimethylammonium, dimethyldiallylammonium. The marketed products meeting this definition are more particularly the products sold under the name "Celquat® L 200" and "Celquat® H 100" by the National Starch Company.

Preferably, the polysaccharide(s) are chosen from scleroglucan gums, cellulose polymers, xanthan gums, guar gums, preferentially from scleroglucan gums, guar gums and cellulose polymers.

The polysaccharide(s) may be present in the coloring composition used in the process according to the invention in a content ranging from 0.001 to 5% by weight and preferably from 0.01 to 4%, and more preferably from 0.05 to 3% by weight relative to the total weight of the coloring composition.

The coloring composition according to the invention may comprise water or a mixture of water and optionally one or more solvents other than the compounds of formula (I) and C ₂ -C ₆ hydroxylated aliphatic solvents such as polyol ethers such as dipropylene glycol monomethyl ether.

Preferably, the coloring composition comprises water, preferably in a content ranging from 20 to 95% by weight, preferably from 30 to 80% by weight, and even more preferably from 40 to 87% by weight relative to the total weight of the coloring composition.

The coloring composition used in the process of the invention may also contain various adjuvants conventionally used in compositions for coloring hair, such as anionic, cationic, non-ionic, amphoteric or zwitterionic surfactants; anionic, cationic, amphoteric, zwitterionic or non-ionic polymers other than polysaccharides; mineral or organic thickening agents; antioxidants, penetrating agents, sequestering agents, perfumes, buffers, dispersing agents, conditioning agents, film-forming agents, ceramides, preservatives, opacifying agents.

The above adjuvants are generally present in an amount for each of them between 0.01 and 20% by weight relative to the weight of the coloring composition.

Of course, those skilled in the art will take care to choose this or these possible complementary compounds in such a way that the advantageous properties intrinsically attached to the coloring composition are not, or not substantially, altered by the addition(s) envisaged.

The pH of the coloring composition used in the process according to the invention is generally between approximately 2 and 14, and preferably greater than 5. According to a particular embodiment, the pH is between 2.5 and 10. It can be adjusted to the desired value using acidifying or alkalizing agents usually used in dyeing keratin fibers or even using conventional buffer systems.

Among the acidifying agents, we can cite, for example, mineral or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid, lactic acid, sulfonic acids.

Examples of alkalizing agents include ammonia, alkali carbonates, alkanolamines such as mono-, di- and triethanolamines and their derivatives, sodium or potassium hydroxides and compounds of the following formula:

in which W is a propylene residue optionally substituted by a hydroxyl group or a C ₁ -C ₄ alkyl radical; Ra, Rb, Rc and Rd, identical or different, represent a hydrogen atom, a C ₁ -C ₄ alkyl or C ₁ -C ₄ hydroxyalkyl radical.

Process

The process for coloring keratin fibers according to the invention comprises the application to said keratin fibers of the lightening composition described above, and of the coloring composition described above.

Preferably, the step of applying the coloring composition is carried out after the step of applying the lightening composition.

Preferably, the coloring process comprises, before the step of applying the lightening composition to the keratin fibers, a step of mixing an oxidizing composition comprising the chemical oxidizing agent(s) as described previously with an alkaline composition comprising the alkaline agent(s) as described previously to obtain the lightening composition.

This mixing step is preferably carried out at the time of use, just before applying the lightening composition resulting from the mixture to the keratin fibers.

Preferably, the alkaline and oxidizing compositions are mixed in an alkaline composition/oxidizing composition weight ratio ranging from 0.1 to 2, preferably from 0.3 to 1.5, better still from 0.5 to 1.

The lightening composition can be applied to dry or wet keratin fibers.

The lightening composition is left on the fibers for a period of time generally ranging from 1 minute to 1 hour, preferably from 5 minutes to 55 minutes.

Preferably, the keratin fibers are then rinsed with water, and possibly washed with shampoo followed by rinsing with water, before possibly being wrung out, dried or left to dry.

The coloring composition is then applied to dry or wet keratin fibers.

The coloring composition is left in place on the fibers for a period of time generally ranging from 1 minute to 100 minutes, preferably from 5 minutes to 80 minutes.

At the end of the treatment, the keratin fibers are possibly rinsed with water, possibly washed with shampoo followed by rinsing with water, before being dried or left to dry.

The invention also relates to a process for coloring keratin fibers, in particular human keratin fibers such as hair, comprising
the application on said keratin fibers:
(i) a lightening composition comprising:
- one or more oxidizing agent(s),
- one or more alkaline agent(s); then
ii) a coloring composition comprising:
- one or more direct dye(s),
- one or more compound(s) of formula (I):
(I)
in which Y represents a C1-C4 hydroxyalkyl group or a C1-C4 hydroxyalkyloxy radical, n denotes an integer ranging from 0 to 5, X, identical or different, represents a C1-C4 alkyl radical or a halogen,
- one or more aliphatic hydroxylated solvent(s) comprising from 2 to 6 carbon atoms.

The invention also relates to a process for coloring keratin fibers, in particular human keratin fibers such as hair, comprising:
1) mixing an oxidizing composition comprising one or more chemical oxidizing agent(s) with an alkaline composition comprising one or more alkaline agent(s) to obtain a lightening composition, then
2) application to said keratin fibers:
i) the lightening composition; then
ii) a coloring composition comprising:
- one or more direct dye(s),
- one or more compound(s) of formula (I):
(I)
in which Y represents a C1-C4 hydroxyalkyl group or a C1-C4 hydroxyalkyloxy radical, n denotes an integer ranging from 0 to 5, X, identical or different, represents a C1-C4 alkyl radical or a halogen,
- one or more aliphatic hydroxylated solvent(s) comprising from 2 to 6 carbon atoms.

Kit

Another subject of the invention is a device with at least three compartments, for coloring keratin fibers, comprising at least a first compartment containing a coloring composition comprising one or more direct dye(s), one or more compound(s) of formula (I) as defined above and one or more aliphatic hydroxylated solvent(s) comprising from 2 to 6 carbon atoms, at least a second compartment containing an alkaline composition comprising one or more alkaline agent(s), and at least a third compartment containing an oxidizing composition comprising one or more chemical oxidizing agent(s).

The compositions of the device according to the invention are packaged in separate compartments, accompanied, if necessary, by appropriate application means, identical or different, such as brushes, brushes or sponges.

The device mentioned above can also be equipped with a means for delivering the desired mixture to the hair, for example such as the devices described in patent FR 2586913.

The following examples serve to illustrate the invention without, however, being limiting in nature.

Examples

In the following examples, all quantities are indicated as a percentage by mass of active ingredient (AI) relative to the total weight of the composition (unless otherwise stated).

Compositions

Compositions A, C and O were prepared from the compounds whose contents are indicated in the tables below:

Alkaline composition A

HAS ETHANOLAMINE 12.9 LAURIC ACID 3.0 GLYCOL DISTEARATE 2.0 CETEARYL ALCOHOL 11.5 PROPYLENE GLYCOL 10.0 Oxyethylenated fatty alcohols 20.0 POLYQUATERNIUM-22 1.5 HEXADIMETHRIN CHLORIDE 3.0 CARBOMER 0.4 ASCORBIC ACID 0.25 SODIUM METABISULPHITE 0.7 Sequestering agent 0.2 pH adjuster Qs pH = 10.4 +/- 0.4 Water Qs 100

Oxidizing composition O

O HYDROGEN PEROXIDE 6.00 TRIDECETH-2 CARBOXAMIDE MEA 0.82 GLYCERIN 0.50 CETEARYL ALCOHOL 2.28 CETEARETH-25 0.57 PHOSPHORIC ACID Qs pH = 2.2 +/- 0.2 Stabilizing agents, sequestering agents Qs Water Qs 100

Coloring composition C

C BENZYL ALCOHOL 2.0 ethanol 8.0 BASIC RED 76 0.5 BASIC BROWN 17 0.5 BASIC YELLOW 57 0.6 HC BLUE NO.16 0.7 SCLEROTIUM GUM 2.0 Sequestering agent 0.5 pH adjuster Qs pH = 7 +/- 0.2 Water Qs 100

The method according to the invention (Protocol 1) comprising the application of a lightening composition followed by the application of a coloring composition was compared to a method which only comprises the application of the coloring composition, without first applying the lightening composition (Protocol 2).

Protocol 1 (invention)

At the time of use, the alkaline composition A was mixed with the oxidizing composition O according to the weight ratio 1+1.5 to obtain a lightening composition.

The lightening composition obtained was then applied to a strand of 90% natural white hair at a rate of 5g of mixture/g of hair.

After 35 minutes of application on a plate set to 27°C, the hair was rinsed, washed with a standard shampoo, and air dried.

Coloring composition C was then applied to the strands at a rate of 5g of mixture /g of hair.

After a 60-minute application time at 27°C under an occlusive cellophane system, the strands were rinsed, then washed and dried using a hair dryer.

The locks of hair thus colored were then subjected to a washing test with shampoo in order to evaluate the tenacity (remanence) of the coloring obtained.

Protocol 2 (comparative)

Coloring composition C was applied to a strand of 90% natural white hair at a rate of 5g of mixture /g of hair.

After a 60-minute application time at 27°C under an occlusive cellophane system, the strands were rinsed, then washed and dried using a hair dryer.

The locks of hair thus colored were then subjected to a washing test with shampoo in order to evaluate the tenacity (remanence) of the coloring obtained.

Results

Colorimetric measurements were performed using a KONICA MINOLTA-3600 spectrocolorimeter (illuminant D65, angle 10°, specular component included) in the CIELab system.

In this L*a*b* system, L* represents the intensity of the color, a* indicates the green/red color axis and b* the blue/yellow color axis. The lower the value of L*, the more intense, powerful the color.

L* Protocol 1 (invention) 20.65 Protocol 2 (comparative) 24.19

The hair strands treated with the lightening step before the coloring step according to the invention have a lower L* value than those treated only with the coloring step according to the comparison.

In other words, the process according to the invention makes it possible to obtain a more intense coloring than the comparative process.

Color remanence.

Color retention is assessed by the color difference ΔE between the colored strands before washing and after washing. The lower the ΔE value, the more the color will persist after shampooing. The ΔE value is calculated using the following equation:

In this equation, L*a*b* represent the values measured after hair coloring and after washing, and L ₀ *a ₀ *b ₀ * represent the values measured after hair coloring but before washing.

L* has* b* ΔE Protocol 1 (invention) Before washing 20.65 0.15 2.37 3.11 After washing 23.16 1.79 3.21 Protocol 2 (comparative) Before washing 24.19 2.11 4.68 6.25 After washing 29.67 2.31 7.68

The hair strands treated with the lightening step preceding the coloring step according to the invention have a lower ΔE value than those treated only with the coloring step according to the comparison.

In other words, the process according to the invention makes it possible to obtain better color retention after washing with shampoo compared to the comparative process.

Claims (15)

Process for coloring keratin fibers, in particular human keratin fibers such as hair, comprising the application to said keratin fibers:
(i) a lightening composition comprising:
- one or more oxidizing agent(s),
- one or more alkaline agent(s); and
ii) a coloring composition comprising:
- one or more direct dye(s),
- one or more compound(s) of formula (I) :
(I)
in which Y represents a C ₁ -C ₄ hydroxyalkyl group or a C ₁ -C ₄ hydroxyalkyloxy radical, n denotes an integer ranging from 0 to 5, X, identical or different, represents a C ₁ -C ₄ alkyl radical or a halogen,
- one or more aliphatic hydroxylated solvent(s) comprising from 2 to 6 carbon atoms. Coloring process according to the preceding claim, in which the coloring composition comprises one or more cationic direct dye(s), preferably chosen from azo cationic direct dyes, hydrazono cationic direct dyes, anthraquinone cationic direct dyes, and mixtures thereof. Dyeing process according to any one of the preceding claims, in which the total content of the direct dye(s) ranges from 0.001 to 20%, preferably from 0.005 to 15% by weight, more preferably from 0.01 to 10% by weight, better still from 0.05 to 5% by weight, even better still from 0.1 to 3% by weight, relative to the total weight of the dyeing composition. Coloring process according to any one of the preceding claims in which the compound(s) of formula (I) are chosen from benzyl alcohol, phenyl ethanol, phenoxyethanol, preferably benzyl alcohol. Dyeing process according to any one of the preceding claims, in which the total content of the compound(s) of formula (I) in the dyeing composition ranges from 0.01 to 10% by weight, preferably from 0.05 to 8% by weight, better still from 0.1 to 5% by weight relative to the weight of the dyeing composition. Dyeing process according to any one of the preceding claims in which the C ₂ -C ₆ hydroxylated aliphatic solvent(s) are chosen from ethanol, glycerol, propylene glycol, dipropylene glycol, hexylene glycol, preferably ethanol and/or hexylene glycol, preferably ethanol. Dyeing process according to any one of the preceding claims, in which the total content of the C ₂ -C ₆ hydroxylated aliphatic solvent(s) ranges from 0.1% to 40% by weight, preferably from 0.5 to 30% by weight, more preferably from 1 to 20% by weight, better still from 2 to 15% by weight, even better still from 3 to 10% by weight, relative to the weight of the dyeing composition. Dyeing process according to any one of the preceding claims in which the weight ratio of compounds of formula (I)/C ₂ -C ₆ hydroxylated aliphatic solvent(s) is less than or equal to 1, preferably ranges from 0.1 to 1, better still from 0.1 to 0.5. A coloring process according to any one of the preceding claims, wherein the chemical oxidizing agent(s) are chosen from hydrogen peroxide, urea peroxide, alkali metal bromates or ferricyanides, peroxygenated salts such as alkali or alkaline earth metal persulfates, perborates and percarbonates, and peracids and their precursors; preferably hydrogen peroxide. A coloring method according to any one of the preceding claims, wherein the lightening composition does not comprise peroxygenated salts. Dyeing process according to any one of the preceding claims, in which the alkaline agent is chosen from alkanolamines such as monoethanolamine, diethanolamine, triethanolamine; ammonia, carbonates or bicarbonates such as sodium (hydrogen)carbonate and potassium (hydrogen)carbonates, silicates or metasilicates of alkali or alkaline earth metals such as sodium metasilicate and mixtures thereof, more preferably from alkanolamines and ammonia, better still from alkanolamines, even better still, monoethanolamine. A coloring method according to any one of the preceding claims, wherein the step of applying the coloring composition ii) is carried out after the step of applying the lightening composition i). Coloring process according to any one of the preceding claims, which comprises, before step i), a step of mixing an oxidizing composition comprising the chemical oxidizing agent(s) with an alkaline composition comprising the alkaline agent(s) to obtain the lightening composition. Dyeing process according to any one of the preceding claims which comprises a step of rinsing the keratin fibers between steps i) and ii). Device with at least three compartments, for coloring keratin fibers, comprising at least a first compartment containing a coloring composition as defined in any one of claims 1 to 8, at least a second compartment containing an alkaline composition comprising one or more alkaline agent(s), preferably as defined in claim 11, and at least a third compartment containing an oxidizing composition comprising one or more chemical oxidizing agent(s) as preferably defined in claim 9.